2 Workshop on Fats and Oils as Renewable Feedstock for ... - abiosus

abiosus e.V.
Non-Profit Association for the Advancement of Research on Renewable Raw Materials
2 nd <strong>Workshop</strong> on
Fats and Oils as Renewable Feedstock
for the Chemical Industry
Program
Abstracts
List of Participants
22. - 24. March 2009
Emden, Germany
in Cooperation with:
University of Applied Sciences OOW
German Society for Fat Science (DGF)
Agency of Renewable Resources (FNR)

Scientific and Organizing Committee
Jürgen O. Metzger, abiosus e.V., and University of Oldenburg
Michael A. R. Meier, University of Applied Sciences OOW
Acknowledgement
Financial Support by the German Federal Ministry of Nutrition, Agriculture and Consumer
Protection (BMELV) is gratefully acknowledged.
2

Content
Program 5
Poster session 10
Abstracts of lectures 13
Abstracts of posters 42
List of participants 76
3

Program
Lectures and Posters
5

Sunday, 22. March 2009
Registration
Registration will be opened from 13:00 - 19:00
15:30
Welcome and Opening
Jürgen O. Metzger, abiosus
Uwe Bornscheuer, President of German Society for Fat Science
Manfred Weisensee, Vicepresident of University of Applied Sciences OOW
Norbert Holst, Agency for Renewable Resources (FNR)
Use of renewable raw materials in industry and funding of research and
development in this field
16:00 – 18:00
1. Session: Joel Barrault, Chair
16:00 Vegetable oils as raw materials for industrial applications
L1 Karlheinz Hill, Cognis, Germany
16:30 Carbonylation as a route to chemicals from biomass
L2 David Cole-Hamilton, Cristina Jimenez-Rodriguez, W. Roy Jackson, Yulei Zhu,
University of St. Andrews, School of Chemistry, St Andrews, UK
17:00 Metathesis with oleochemicals: a sustainable match to obtain monomers
and polymers from renewable resources
L3 Michael A. R. Meier, University of Applied Sciences OOW, Emden, Germany
17:30 Biocatalysis in the modification of fats and oils for oleochemistry
L4 Uwe Bornscheuer, Institute of Biochemistry, Greifswald University, Greifswald,
Germany
18.00 - 20.00
Poster session and opening mixer
Posters will be displayed until the end of the workshop.
6

Monday, 23. March 2009
9:00 – 10:30
First Morning Session: George John, Chair
09:00 Catalytic functionalisation of fatty compounds
L5 Jessica Pérez Gomes, and Arno Behr, University of Dortmund, Germany
09:30 Oxidation of tensidic alcohols to their corresponding carboxylic acids via
Au- and AuPt-catalysts
L6 Ulf Prüße, Katharina Heidkamp, Nadine Decker, Kerstin Martens, Klaus-Dieter
Vorlop, Oliver Franke, and Achim Stankowiak, Johann Heinrich von Thünen-
Institut (vTI), Braunschweig, Germany
09:50 Plant oils as precursors of N-containing compounds via alkene metathesis
L7 Christian Bruneau, Pierre H. Dixneuf, Raluca Malacea, Cédric Fischmeister,
Xiaowei Miao, Institut Sciences Chimiques de Rennes, University of Rennes 1,
Rennes, France
10:10 Phytomining of plant enzymes for biotechnological use of fats and oils
L8 Andreas Müller, and Guido Jach, Phytowelt GreenTechnologies GmbH, Nettetal,
Germany
10:30 – 11:00 Coffee break
11:00 -12:20
Second morning session: Zoran Petrovic, Chair
11:00 Rational design of solid catalysts for selective glycerol activations
L9 François Jerome, and Joel Barrault, CNRS/LACCO, Poitiers, France
11:30 Acid-catalysed rearrangement of fatty epoxides: perspectives in application
of acid saponites
L10 Matteo Guidotti, Nicoletta Ravasio, Rinaldo Psaro, Maila Sgobba, Chiara Bisio,
Fabio Carniato, and Leonardo Marchese, CNR-ISTM, Milan, Italy
11:50 Fatty acids: safe and versatile building blocks for the chemical industry
L11 Peter Tollington, Croda, Gouda, The Netherlands
12:20 – 13:30 Lunch break
7

13:30 – 14:50
First afternoon session: Selim Küsefoglu, Chair
13:30 Lipids and Lipases - Combination Products From Renewables
L12 Manfred P. Schneider, Matthias Berger, Kurt E. Laumen, Guido Machmüller,
Stefan Müller, and Claudia Waldinger, University of Wuppertal, Wuppertal,
Germany
14:00 O-Acylated Hydroxy carboxylic acid anhydrides: Novel Building Blocks for
Surfactants and Emulsifiers
L13 Bernd Jakob, Hans-Josef Altenbach, Manfred Schneider, Karsten Lange, Rachid
Ihizane, Zeynep Ylmaz, and Sukhendu Nandi, University of Wuppertal, Wuppertal,
Germany
14:20 Biocompatible surfactants from renewable hydrophiles
L14 Maria Rosa Infante, Lourdes Perez, MCarmen Moran, Ramon Pons, and Aurora
Pinazo, IQAC - CSIC, Barcelona, Spain
14:50 – 15:20 Coffee break
15:20 – 17:30
Second afternoon session: Marina Galià, Chair
15:20 Gemini-Tensides and Ion Channels from Fatty acids
L15 M. Dierker, and Hans J. Schäfer, University of Münster, Münster,
Germany
15:50 Aliphatic ß-Chlorovinylaldehydes as versatile building blocks in syntheses
of heterocycles
L16 Annett Fuchs, Dieter Greif, and Melanie Kellermann, University of Applied
Sciences, Zittau, Germany
16:10 Calendula Oil as Paint Additive
L17 Ursula Biermann (a), Werner Butte (a), Ralf Holtgrefe (b), Willi Feder (b), and
Jürgen O. Metzger (a), (a) University of Oldenburg, Oldenburg, Germany, (b) bio
pin, Jever, Germany
16:30 Crops: A Green Approach toward Self-Assembled Soft Materials
L18 George John, City College of City University of New York, New York, USA
17:00 Exploiting vegetable oils for the delivery of hydrophilic drugs
L19 Sarina Grinberg, Charles Linder, and Eliahu Heldman, Ben-Gurion University of
the Negev, Beer-Sheva, Israel
19:30 Conference dinner Upstalsboom Parkhotel
8

Tuesday, 24. March 2009
09:00 – 10:30
First morning session: Maria Rosa Infante, Chair
09:00 The role of renewable resources for Bayer Material Science
L20 Ralf Weberskirch, Bayer Materials Science, Leverkusen, Germany
09:30 Vegetable oil-based triols from hydroformylated fatty acids and
polyurethane elastomers
L21 Zoran Petrovic, Ivana Cvetkovic, DooPyo Hong, Xianmei Wan, Wei Zhang,
Timothy Abraham, and Jeffrey Malsam, Pittsburg State University, Kansas
Polymer Research Center, Pittsburg, Kansas, USA
10:00 New approaches to polymers and composites from plant oils
L22 Selim Küsefoglu, Bogazici University Chemistry Department, Istanbul, Turkey
10:30 – 11:00 Coffee break
11:00 -13:15
Second morning session: Michael A.R. Meier, Chair
11:00 Vegetable-oil based thermosetting polymers
L23 Marina Galià, Joan Carles Ronda, Gerard Lligadas, Virginia Cádiz, University
Rovira i Virgili Tarragona, Spain
11:30 Chemo-enzymatic synthesis of oil polyols and polyurethanes of them
L24 Tomas Vlcek, SYNPO, Pardubice, Czech Republic
11:50 Study of ASA (alkenyl succinic anhydrides) from fatty acid esters of
vegetable oils as paper sizing agents
L25 Laure Candy, Carlos Vaca-Garcia, Elisabeth Borredon, Laboratoire de Chimie
AgroIndustrielle; ENSIACET, Toulouse, France
12:10 Use of vegetable oil based thermosetting resins in compound stone
technology
L26 Stefano Zeggio, Fabio Bassetto, Breton Research Centre, Castello di Godego,
Italy
12:30 Life cycle assessment of high performance polyamides
L27 Georg Oenbrink, Martin Roos, Franz-Erich Baumann, Harald Häger, Evonik
Degussa GmbH, Marl, Germany
13:00 - 13:15 Best poster award
Uwe Bornscheuer, European Journal of Lipid Science and Technology, Editor-in-Chief
Closing remarks, Michael A. R. Meier, University of Applied Sciences OOW
9

Poster
P1 Catalytic cleavage of methyl oleate or oleic acid
A. Köckritz 1 , M. Blumenstein 2 , A. Martin 1
1 Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Berlin, Germany
2 Hobum Oleochemicals GmbH, Hamburg, Germany
P2 Heterogeneously catalyzed hydrogen-free deoxygenation of saturated C8,
C12 and C18 carboxylic acids
S. Mohite, U. Armbruster, M. Richter, D.L. Hoang, and Andreas Martin, Leibniz-
Institut für Katalyse e.V. an der Universitaet Rostock, Berlin, Germany
P3 Flame retardant polyesters from renewable resources via ADMET
Lucas Montero de Espinosa, Joan Carles Ronda, Virginia Cádiz, Universitat
Rovira i Virgili, Tarragona, Spain, and Michael A. R. Meier, University of Applied
Sciences OOW, Emden, Germany
P4 Catalytic access to bifunctional products from plant oil derivatives
Xiaowei Miao, C. Fischmeister, C. Bruneau, P. H. Dixneuf, Institut Sciences
Chimiques de Rennes, Rennes, France
P5 Synthesis and Characterization of Surfactants from Renewable Resources
Rachid Ihizane, Bernd Jakob, Karsten Lange, Zeyneb Yilmaz, Sukhendu Nandi,
Manfred P. Schneider and Hans. J. Altenbach, Fachbereich C – Mathematik und
Naturwissenschaft, Fachgruppe Chemie, Bergische Universität Wuppertal,
Wuppertal, Germany
P6 Synthesis of bifunctional monomers via homometathesis of fatty acid
derivatives
Jürgen Pettrak, Herbert Riepl, Martin Faulstich, and Wolfgang A. Herrmann, TU
München, Lehrstuhl für Rohstoff und Energietechnologie, Straubing, Germany
P7 Synthesis and evaluation of value added products from Glycerol
Avinash Bhadani, and Sukhprit Singh, Guru Nanak Dev University, Department of
Chemistry, Amritsar, India
P8 New Polymers from Plant Oil Derivatives and Styrene-Maleic Anhydride
Copolymers
Cem Öztürk, and Selim Küsefoğlu, Bogazici University, Chemistry Department,
Istanbul, Turkey
P9 Chain Extension Reactions of Unsaturated Polyesters with Epoxidized
Soybean Oil
Ediz Taylan, and Selim Küsefoglu, Bogazici University, Chemistry Department,
Istanbul, Turkey
P10 Soybean Oil Based Isocyanates: Synthesis, Characterizations and
Polymerizations
Gökhan Çaylı, and Selim Küsefoğlu, Bogazici University, Chemistry Department,
Istanbul, Turkey
10

P11 Aliphatic ß-chlorovinylaldehydes as versatile building blocks in syntheses
of heterocycles
Annett Fuchs, Dieter Greif, and Melanie Kellermann, University of Applied
Siences, Zittau, Germany
P12 Syntheses and reaction behavior of long-chained alkyl methyl ketones
starting from fatty acids, fatty alcohols and fatty nitriles
Melanie Kellermann, Annett Fuchs, Dieter Greif, University of Applied Sciences,
Zittau, Germany
P13 Hydrophobic modification of Inulin in aqueous media using alkyl epoxides
and basic catalysis
Jordi Morros, Bart Levecke, and Mª Rosa Infante, IQAC - CSIC, Barcelona, Spain
P14 Short Chain Sugar Amphiphiles: Alternative Oil Structuring Agents
Swapnil R Jadhav, Praveen Kumar Vemula, and George John, City College of
City, University of New York, New York, USA
P15 Novel enzymes for lipid modification
H. Brundiek, R. Kourist, M. Bertram, and U. Bornscheuer, University of
Greifswald, Germany
P16 Production of fine and bulk chemicals using silage as a renewable resource
Tim Sieker, and Roland Ulber, University of Kaiserslautern, Kaiserslautern,
Germany
P17 Enzymatic degradation of pre-treated wood
Sebastian Poth, Magaly Monzon, Nils Tippkötter, and Roland Ulber, University of
Kaiserslautern, Germany
P18 PA X,20 from renewable resources via metathesis and catalytic amidation
Hatice Mutlu,and Michael A.R. Meier, University of Applied Sciences OOW,
Emden, Germany
P19 DERIVATIVES OF VEGETABLE OILS AS COMPONENTS OF HYDRAULIC
FLUIDS
Talis Paeglis, Aleksejs Smirnovs, Rasma Serzane, Maija Strele, Mara Jure, Riga
Technical University, Riga, Latvia
P20 ULTRASOUND PROMOTED ETHANOLYSIS OF RAPESEED OIL
Pavels Karabesko, Maija Strele, Rasma Serzane, Mara Jure, Riga Technical
University, Riga, Latvia
P21 From Glycerine via Acetals to new Amphiphils
J. Baumgard (a,b) , E. Paetzold (a), and U. Kragl (a,b), (a) Leibniz-Institut für
Katalyse an der Universität Rostock e.V., Rostock, b) Institut für Chemie,
Universität Rostock e. V., Rostock
P22 BIOBASED SEGMENTED POLYURETHANES FROM METHYL OLEATE
BASED POLYETHER POLYOLS
Enrique del Río, Virginia Cádiz, Marina Galià, Gerard Lligadas, Joan Carles
Ronda, Universitat Rovira i Virgili, Tarragona, Spain
11

P23 DETAILED STUDIES OF SELF- AND CROSS-METATHESIS REACTIONS OF
FATTY ACID METHYL ESTERS
Guy B. Djigoue, and Michael A. R. Meier, University of Applied Sciences OOW,
Emden, Germany
P24 Temperature dependant double bond isomerization side reactions during
ADMET polymerizations studied with a monomer from renewable resources
Patrice Aimé Fokou, and Michael A. R. Meier, University of Applied Sciences
OOW, Emden, Germany
P25 Reducing the Environmental Impact of Olefin Metathesis Reactions
Manuela Kniese, Michael A. R. Meier, University of Applied Sciences OOW,
Emden, Germany
P26 An approach to renewable Nylon-11 and Nylon-12 via olefin crossmetathesis
Tina Jacobs, Michael A. R. Meier, University of Applied Sciences OOW, Emden,
Germany
P27 Ultrasonic assisted finishing of cellulose fiber by fatty acid amide
derivatives
Mazeyar Parvinzadeh, Mohammad Shaver, and Bashir Katozian, Islamic Azad
University, Shahre rey branch, Tehran, Islamic Republic of Iran
P28 Hydrolysis of nylon 6 with proteolytic enzyme
Mazeyar Parvinzadeh, Islamic Azad University, Shahre rey branch, Tehran,
Islamic Republic of Iran
P29 Comparing finishing of polyester fibers with micro and nano emulsion
silicones
Mazeyar Parvinzadeh, Islamic Azad University, Shahre rey branch, Tehran,
Islamic Republic of Iran
P30 PIBOLEO project: Eco Innovative process for multi-functional bi-
oleothermal teatment for wood preservation and fire proofing
Sandra Warren, Carine Alfos, and Frédéric Simon, ITERG, Pessac, France
P31 Cellulases in bi-phasic media
Nathalie Berezina, Joel Nys, and Laurent Paternostre, Natiss - Materia Nova,
7822 Ghislenghien, Belgium
12

Abstracts
Part 1: Lectures
13

L1 Vegetable oils as raw materials for industrial applications
14
Karlheinz Hill, Cognis, Germany
Karlheinz.Hill@cognis.com
Natural fats and oils, carbohydrates and proteins are key raw materials for the chemical
industry using renewable resources. Although in general, biomass is available in large
amounts (e.g. cellulose), the annual production volumes of selected biobased commodities
are still small compared to coal or crude oil.
Annual production of commodities worldwide (2004, million tons) a
Wheat Rice Starch Sugar b Fats&Oilsc Crude Oil Coal d
610 610 40 145 131 3600 3800
a) sources: OilWorld, USDA, Industrieverband Agrar, Wikipedia; b) from beet and cane;
c) vegetable and animal based; d) as SKE (1 kg SKE = 0,984 kg bituminous coal)
Until now, availability and use was quite balanced and the quantities could be adjusted
according to different demands. For example, in the case of natural oils and fats, the
production volume was steadily increased from 30 million tons in 1960 to 131 million tons
in 2004. Most of it was used for food (81% in 2004), a minor amount for animal feed (6% in
2004) and chemistry (10% in 2004). However, what we have observed for some time is a
shift towards an increasing use of renewable raw materials for bioenergy and biofuels. In
the case of natural vegetable oils, the expected share for energy is estimated to grow to
15% (!) of the total annual capacity in 2012 compared to 3% in 2004. This is one
consequence of political measures such as the European Biofuel Directive 2003/30/EC.
Biodiesel production volumes were expanded significantly in the recent past and this trend
is expected to continue in Europe and other regions such as South East Asia, South
America and India, with a further increase in production capacities forecasted at least for
the next 5-10 years.
When the so-called 2nd generation products, such as sundiesel or biomass-to-liquid fuels,
are ready to be launched on the market, the demand on fats and oils for biofuels might
decrease again. These new technologies are definitely needed assuming that even with
increasing production volumes for fats and oils, the future bioenergy and biofuel demand
cannot be satisfied by this source alone.
In the meantime, the high demands for biodiesel, still further stimulated by subsidies, will
create strong competition with the established uses for vegetable oils for nutrition and also
for the chemical industry (oleochemistry). A very similar situation is being observed in the
case of bioethanol from carbohydrates and/or sugar. The competition between the use of
agricultural products for nutrition and energy is one of the reasons why market prices of
such agricultural commodities are recently subject of extremely high volatility. Other
reasons are the increasing demand for food in various regions of the earth, crop yield, and
financial speculations by investment funds.
The use of renewable resources is only one important part of the future "green" strategy in
industry. What must also be considered are sustainability practices across the entire value
chain. This strategy is already applied to palm oil. It is the first time an expert group (The
Round Table of Sustainable Palm Oil, RSPO) involving all participants in the industrial
agricultural commodity value chain has defined what sustainable agriculture really should
mean. The challenging goal to develop, implement and verify credible global standards for
sustainable palm oil products has finally been achieved. The principles and criteria for
sustainable palm oil are in the implementation process and this year the first products are
available according to the standards. Cognis was the first chemical supplier in membership
and is until today one of the few. Its expertise in natural raw materials enables Cognis to
develop concepts with its customers on how to make renewable raw materials sustainable
as almost all of its raw materials from the palm tree are being sourced from RSPO
members.

L2
Carbonylation as a route to chemicals from biomass
David Cole-Hamilton, Cristina Jimenez-Rodriguez, W. Roy Jackson, and Yulei Zhu,
University of St. Andrews, School of Chemistry, St Andrews, UK
djc@st-and.ac.uk
As oil stocks dwindle and become increasingly expensive, it will become essential to
develop routes to chemicals starting from feedstocks that can be derived from plant
sources. One interesting group of chemicals is the diesters. Especially desirable are the
alpha-omega diesters since they are used in a wide variety of polyesters for use in plastic
bottles, synthetic carpets and speciality plastics. We have been developing a range of
palladium based catalysts that can form alpha-omega diesters from unsaturated esters by
methoxycarbonylation reactions. When these catalysts are applied to methyl oleate,
dimethyl 1,19-nonadecanedioate is formed in high selectivity. This remarkable reaction
involves isomerisation of the double bond to the end of the chain and, only when it is there,
is it carbonylated. The same product is formed from methyl linoleate and methyl linolenate.
Since shorter chain length diesters are often required, the group of W. R. Jackson in
Monash Australia has coupled this isomerisation carbonylation reaction with metathesis of
the original oil with butene. The metathesis shortens the chain to give an unsaturated ester
which can be isomerised and carbonlyated to give shorter alpha-omega diesters. We shall
discuss the nature of the catalysts and the reasons for their very specific actions.
15

L3
16
Metathesis with oleochemicals: a sustainable match to obtain
monomers and polymers from renewable resources
Michael A. R. Meier, University of Applied Sciences OOW, Emden, Germany
michael.meier@fh-oow.de
In ages of depleting fossil reserves and increasing emission of green house gases it is
obvious that the utilization of renewable feedstocks is one necessary step towards a
sustainable development of our future. Especially plant derived oils bear a large potential
for the substitution of currently used petrochemicals, since a variety of value added
chemical intermediates can be derived from these resources in a straightforward fashion
taking full advantage of nature's synthetic potential. Here, new approaches for the
synthesis of monomers as well as polymers from plant oils as renewable resources[1] via
olefin metathesis[2,3] will be discussed. As an example, we recently showed that different
chain length α,ω-diester monomers can be obtained from plant oil derived fatty acid esters
via olefin cross-metathesis[4] with methyl acrylate taking advantage of natures "synthetic
pool" of fatty acids with different chain lengths and positions of double bonds.[5]
Similarly, we could show that the cross-metathesis with allyl chloride and other functional
olefins allows for the synthesis of α,ω-difunctional compounds.[6,7] Therefore, this strategy
offers the possibility to introduce a variety of different functional groups to the ω -position
of fatty acid derivatives, thus providing valuable starting materials for a variety of
polyesters and polyamides.
Moreover, acyclic diene metathesis (ADMET), can be used to directly obtain
macromolecules from such starting materials. The ADMET polymerization [8] of undecyl
undecenoate, for instance, led to high molecular weight polyesters.[9] It was possible to
effciently control the molecular weight of these materials and to prepare telechelics via the
application of mono-functional chain-stoppers.[9] More interestingly, this approach can
also be used to prepare ABA triblock copolymers with control of the degree of
polymerization (DP) of the B block in a single reaction step.[9] Furthermore, if tri-functional
monomers in combination with chain stoppers are investigated the synthesis of
hyperbranched polymer architectures with functional groups in their periphery can be
achieved in a single reaction step.[10]
Acknowledgement. Financial support from the Fachagentur Nachwachsende Rohstoffe
(FKZ 22026905) is kindly acknowledged.
References
[1] M. A. R. Meier, J. O. Metzger, U. S. Schubert, Chem. Soc. Rev. 2007, 36, 1788.
[2] R. H. Grubbs, Angew. Chem. Int. Ed. 2006, 45, 3760-3765.
[3] A. Rybak, P. A. Fokou, M. A. R. Meier, Eur. J. Lipid Sci. Technol. 2008, 110, 797.
[4] S. J. Connon, S. Blechert, Angew. Chem. Int. Ed. 2003, 42, 1900.
[5] A. Rybak, M. A. R. Meier, Green Chem. 2007, 9, 1356.
[6] A. Rybak, M. A. R. Meier, Green Chem. 2008, 10, 1099.
[7] T. Jacobs, A. Rybak, M. A. R. Meier, Appl. Catal., A 2009, 353, 32.
[8] T. W. Baughman, K. B. Wagener, Adv. Polym. Sci. 2005, 176, 1.
[9] A. Rybak, M. A. R. Meier, ChemSusChem 2008, 1, 542.
[10] P. A. Fokou, M. A. R. Meier, Macromol. Rapid Commun. 2008, 29, 1620.

L4
Biocatalysis in the modification of fats and oils for oleochemistry
Uwe Bornscheuer, Institute of Biochemistry, Greifswald University, Greifswald, Germany
uwe.bornscheuer@uni-greifswald.de
Lipases and related enzymes (esterase, different phospholipases) are currently used as
biocatalysts in a broad range of lipid modifications [1]. In this lecture, the identification of
novel esterases/lipases from the metagenome will be shown highlighting the discovery of
biocatalysts with certain fatty acid chain-length profiles [2]. Furthermore, methods for the
identification and immobilization of desired enzymes using a microtiterplate (MTP) based
method [3, 4] will be presented. An example for protein engineering deals with a lipase
from Rhizopus oryzae (ROL), which was engineered to increase its stability toward lipid
oxidation products such as aldehydes with the aim of improving its performance in
oleochemical industries. Key to success was the saturation mutagenesis of selected Lys
and His residues combined with a MTP-based high-throughput screening of stable variants
[5]. Furthermore, the use of ionic liquids as media for the synthesis of sugar fatty acid
esters will be covered [6].
[1] Bornscheuer U.T. (Ed.) Enzymes in Lipid Modification, Wiley-VCH, Weinheim; Metzger,
J.O., Bornscheuer, U.T. (2006), Appl. Microbiol. Biotechnol., 71, 13-22.
[2] Bertram, M. Hildebrandt, P., Weiner, D.W., Patel, J. S., Bartnek, F., Hitchman, T.,
Bornscheuer, U.T. (2008), J. Am. Oil Chem. Soc., 85, 47-53
[3] Bertram. M., Manschot-Lawrence, C., Flöter, E., Bornscheuer, U.T. (2007) Eur. J. Lipid
Sci. Technol., 109, 180-185
[4] Brandt, B., Hidalgo, A., Bornscheuer, U.T. (2006), Biotech. J., 1, 582-587.
[5] DiLorenzo, M., Hidalgo, A., Molina, R., Hermoso, J.A., Pirozzi, D., Bornscheuer, U.T.
(2007), Appl. Environm. Microbiol. 73, 7291-7299.
[6] Ganske, F., Bornscheuer, U.T. (2005), J. Mol. Catal. B: Enzym., 36, 40-42; Ganske, F.,
Bornscheuer, U.T. (2005), Org. Lett., 7, 3097-3098.
17

L5
18
Catalytic Functionalisation of Fatty Compounds
Jessica Pérez Gomes, and Arno Behr, Chair of Technical Chemistry A, Technical
University Dortmund, Dortmund, Germany
Arno.Behr@bci.tu-dortmund.de
Every year the chemical industry uses about 250 million tons of resources for the
production of organic chemicals. Only 20 millions tons, that means only 8-10 %, are based
on renewable resources, especially on fat and oils. This contribution gives a short
overview about the numerous possibilities to functionalise fatty compounds via
homogeneous transition metal catalysis.
Unsaturated fatty compounds contain one or more C=C-double bonds which can be
easily functionalised via coordination to transition metal complexes [1]. Some important
examples of these functionalisations are epoxidations, dihydroxylations, oxidative
cleavage reactions, hydrosilylations [2-3], hydroformylations [4] and
hydroaminomethylations [5]. Thus new carbon-oxygen-, carbon-silicon-, carbon-carbon-
and carbon-nitrogen-bonds can be formed yielding a broad spectrum of chemical
compounds with new properties and new applications. Further important examples are the
rhodium-catalysed cooligomerisations [6-7] or the ruthenium-catalysed metathesis of fatty
compounds with alkenes.
If fats and oils are transesterified with methanol glycerol is formed as an important byproduct
in oleochemistry. A great number of applications of glycerol are well known, however,
the raising amounts of glycerol because of the enormous production of biodiesel can
not be put into the market. Therefore new reactions are needed to transform glycerol into
new products with new markets. Once again, homogeneous catalysis offers interesting
possibilities [8-9]: Via catalytic oxidations glycerol acid or dihydroxyacetone can be formed.
Dehydratisation yields acrolein which is further oxidised to acrylic acid. Further follow-up
products of glycerol are for instance propanediols, epichlorohydrine, glycerol dimers or
trimers, glycerol carbonate, glycerol acetals or ketals. Another important group of
chemicals are the glycerol ethers, for instance the glycerol tertiary butyl ethers [10] or the
telomers of glycerol [11-14].
____________
References
1. Behr, A.; Westfechtel, A.; Perez Gomes, J; Chemical Engineering and Technology, 2008, 31, 700.
2. Behr, A.; Naendrup, F.; Obst, D.; Eur. J. Lipid Sci. Technol., 2002, 104, 161.
3. Behr, A.; Naendrup, F.; Obst, D.; Adv. Synth. Catal., 2002, 344, 1142
4. Behr, A.; Obst, D.; Westfechtel, A.: Eur. J. Lipid Sci. Technol., 2005, 107, 213.
5. Behr, A. et al.; Eur. J. Lipid Sci. Technol., 2000, 102, 467
6. Behr, A.; Fängewisch, C.; J. Mol. Catal A: Chem, 2003, 197, 115
7. Behr, A.; Miao, Q.; J. Mol. Catal A: Chem, 2004, 222, 127
8. Behr, A.; Eilting, J.; Irawadi, K.; Leschinski, J.; Lindner, F.; Green Chem., 2008, 10, 13.
9. Behr, A.; Eilting, J.; Irawadi, K.; Leschinski, J.; Lindner, F.; Chemistry Today, 2008, 26, 32
10. Behr, A.; Obendorf, L.; Eng. Life Sci., 2003, 2, 185
11. Behr, A.; Urschey, M.; Adv. Synth. Catal., 2003, 345, 1242
12. Behr, A.; Leschinski, J.; Green Chem., 2009, in print
13. Behr, A.: Leschinski, J.; Awungacha, C.; Simic, S.; Knoth, T.; ChemSusChem, 2009,
DOI:10.1002/cssc.200800197
14. Behr, A.; Leschinski, J.; Prinz, A.; Stoffers, M.; Chem. Eng. Proc., submitted

L6
Oxidation of tensidic alcohols to their corresponding carboxylic
acids via Au- and AuPt-catalysts
Ulf Prüße, Katharina Heidkamp, Nadine Decker, Kerstin Martens, Klaus-Dieter Vorlop
Johann Heirich von Thünen-Institut (vTI), Oliver Franke, Achim Stankowiak, Clariant
Deutschland; ulf.pruesse@vti.bund.de
Reducing the use of environmentally hazardous chemicals in industrial processes plays a
key role in the science of catalysis. Particularly the liquid-phase oxidation of tensidic
alcohols to the corresponding carboxylic acids holds a great potential for improvement
towards a “greener” process. Currently ether carboxylic acids are either synthesized via
Williamson’s ether-synthesis using chloroacetic acid derivatives. Incomplete conversion
and consequential excess use of chloroacetic acid lead to impurities (e.g. educt residues
and by-products) which accelerate the deterioration of the acid and impair its solubility. Or
they can be produced by oxidising the corresponding alcohol with dioxygen using
supported Pt- or Pd- catalysts. However, difficulties such as metal leaching and incomplete
conversion may occur during this process. Our research group is first to develop and
employ mono- and bimetallic Au-catalysts for the liquid-phase oxidation of fatty alcohol
ethoxylates and related model compounds, i.e. alkyl ethoxylates and ethoxylates, to their
corresponding carboxylic acid.
Several preparation methods, catalyst supports and Au-Pt-ratios (for bimetallic catalysts)
were screened. For all model compounds monometallic Au-catalysts featured a selectivity
of 100 % to the carboxylic acid. Maintaining total selectivity, the activity could be increased
significantly by using a bimetallic Au-Pt-catalyst with a gold: platinum ratio of 90:10. Thus,
for comparable reaction conditions our catalyst was ten times as active as a Pt-catalyst.
The experiments were carried out at elevated pressures (5-30 bar) in thermostatted
stainless steel autoclaves at constant pH (9 -11). Variation of reaction parameters and
kinetic studies revealed a dependency of the activity on temperature (80 – 130 °C), oxygen
pressure, pH-value and educt concentration (5 – 80 %) – all of which do not affect the
selectivity.
The reaction mechanism should be identical for all model compounds. However, during
the oxidation of certain fatty alcohol ethoxylates with monometallic Au-catalysts
intermediate metal leaching occurs. This phenomenon does not arise with the other two
model compounds. Preliminary results suggest that metal leaching can be reduced
considerably by employing bimetallic catalysts with a proper Au-Pt-ratio.
19

L7
20
Plant oils as precursors of N-containing compounds
via alkene metathesis
Christian Bruneau, Pierre H. Dixneuf, Raluca Malacea Cédric Fischmeister, and Xiaowei
Miao
Institut Sciences Chimiques de Rennes - Catalyse et Organométalliques,
UMR 6226 CNRS-Université de Rennes 1, 35042 Rennes cedex. France
pierre.dixneuf@univ-rennes1.fr
Plant oils, the known precursors of a variety of unsaturated acid derivatives have also the
potential to produce, by action of alkene metathesis catalysis, new intermediates useful for
chemical industry, from renewable materials.
The cross-metathesis, promoted by selected ruthenium catalysts, of unsaturated esters,
acids and other oil derivatives with acrylonitrile and fumaronitrile will be presented [1]
Z or Z Z
CN
+
or NC
CN
Ru Cat
The formed bifunctional compounds are thus the precursors of linear aminoacids and thus
polyamides.
[1] R. Malacea et al, Green Chem., 2009, in press
Z
CN

L8
Phytomining of plant enzymes for biotechnological use of fats and oils
Andreas Müller, and Guido Jach, Phytowelt GreenTechnologies GmbH, Nettetal, Germany
a.mueller@phytowelt.com
Human history is closely linked to the use of plants as valuable sources for nutrition,
commodities and energy as well as a multitude of raw materials, such as fats, oils and
natural polymers like cellulose or starch. However, only recently have we come to see
plants as a cornerstone of sustainable industry by exploiting lead structures and
biosynthetic pathways for the modification of plant derived, renewable resources.
Plant derived fats and oils are already used by the Chemical Industry as renewable
feedstock and unsaturated fatty acids, often found in plant oils, represent well suited raw
materials for the production of polymers, plasticizer and lubricants. Doubtlessly, the wealth
of plant biosynthetic pathways makes plants an attractive source for fascinating new
enzymes for fat and oil modification and biotechnological applications. Use of plant
enzyme and compounds in industrial biotechnology offers new means to address/reach
energy savings and increases of efficiency and sustainability by reducing the number of
steps in processing chains, for example.
Phytowelt GreenTechnologies GmbH excels enzyme discovery via phytomining, a
combinatory high content approach. Our four step integrative approach aims to increase
the efficiency of current production processes, e.g. by complementing microbial production
lines with a suitable gene, or implementing completely new and innovative fermentation
processes. Phytowelt’s approach unlocks the huge potential of plant biodiversity.
Phytowelt’s presentation will introduce its phytomining platform and the power of (plant)
enzymes. Examples for the application of plant enzymes will be given.
21

L9
22
Rational design of solid catalysts for selective glycerol activations
François Jerome, and Joel Barrault, CNRS/LACCO, Poitiers, France
joel.barrault@univ-poitiers.fr
With the aim of finding solutions to the disappearance of fossil raw materials,
scientists focused their attention towards the use of natural products. However, these
products are in most cases polyfunctional and their transformations require the close
control of the chemio- and/or regio- and/or enantioselectivity of processes. To overcome
these problems, catalysis was expected to play a pivotal role by offering to chemists useful
tools for performing selective transformations of renewables to high added value
chemicals. Recent studies clearly showed that inorganic solid supports can directly and
positively impact on the reaction selectivity.
Development of new catalysts with controlled distribution of active sites is probably
one of the most fascinating examples. But a control of the hydrophilicity of catalytic
surfaces is also an important parameter. Playing with the hydrophilic properties of the
catalyst surface, we found that it was possible to limit a lot of secondary reactions allowing
us to transform glycerol with yields and selectivities higher than those obtained with
homogeneous and usual solid acid or basic catalysts.

L10
Acid-catalysed rearrangement of fatty epoxides: perspectives in
application of acid saponites
Matteo Guidotti, Nicoletta Ravasio, Rinaldo Psaro, Maila Sgobba, Chiara Bisio, Fabio
Carniato, and Leonardo Marchese, CNR-ISTM, Milan, Italy
m.guidotti@istm.cnr.it
The ring opening of epoxidized fatty acid derivatives is a valuable transformation for the
production of compounds functionalized on the alkyl chain. Rearranged epoxides could
find applications as precursors of biopolymers, lubricants, polyurethane foams and casting
resins.
A two-step process, starting from fatty acid methyl esters and based uniquely on
heterogeneous and easily recoverable catalysts, is here proposed. The FAME methyl
oleate is epoxidized in liquid phase with tert-butylhydroperoxide in batch reactor over Tigrafted
MCM-41. The transformation is optimized and the conversion attains >90% after
24 h, with selectivity >95% to methyl 9,10-epoxystearate. After separation of the organic
product from the solid Ti-catalyst, the ring opening of the epoxidized fatty ester is
performed in the presence of a protonic acidic saponite clay, obtained by exchanging a
synthetic Na+ saponite in aqueous HCl solutions at different concentrations. The catalytic
results for the nucleophilic addition of methanol to methyl epoxystearate show the good
performance of different acid saponites in terms of activity. The saponite catalysts were
also compared with other widely used heterogeneous systems, such as mesoporous
ordered aluminosilicate Al-SBA-15 and a protonic Beta zeolite (H-BEA). Protonic saponites
showed better results than H2SO4 too (0.45 mmol g -1 ), the typical industrial catalyst for this
reaction.
The best result is obtained over the protonic saponite prepared with a mild pretreatment
(ion exchange in aq. 0.01 M HCl): with methanol, after 5 min, 90% of the epoxide is readily
converted into Me-methoxyhydroxystearate and Me-oxostearate.
23

L11
Fatty acids: safe and versatile building blocks for the chemical industry
24
Peter Tollington, Croda, Gouda, The Netherlands
peter.tollington@croda.com
Fatty acids are basis ingredients for a wide range of consumer and technical products, for
which they provide properties and benefits not readily or economically achieved using
mineral-derived sources.
They can contribute to the development of a more sustainable, biobased economy –not
only through their inherent natural basis, but also through the ability of the fatty acid
producers to handle a wide range of technical/non-edible oil and fat sources and to make
from them high quality, well-defined materials for value-added onward application.
Furthermore, the natural mixtures can be readily purified and separated to yield end
products with precise functionality and properties, distinct from those of the parent
triglyceride compositions.
This talk will outline the processing and chemistry of fatty acids, and illustrate their
versatility as basic building blocks with two contemporary examples ; development of a
synthetic oleochemical wax, and (the properties and benefits provided by) polymerised
fatty acids in a solvent-free coating.

L12
Lipids and Lipases - Combination Products From Renewables
Manfred P. Schneider, Matthias Berger, Kurt E. Laumen, Guido Machmüller, Stefan
Müller, and Claudia Waldinger, University of Wuppertal, Wuppertal, Germany
schneid@uni-wuppertal.de
Agricultural crops represent a considerable reservoir of useful and low cost raw materials
like fats and oils, plant proteins and carbohydrates. By selective combination of their
molecular constituents (e.g. fatty acids, glycerol, amino acids, mono- and disaccharides,
amino sugars etc.) a wide variety of surface active materials can be prepared, all of them -
due to their molecular structures - being potentially highly biodegradable.
Lipases are well established biocatalysts for the selective formation of ester and amide
bonds and thus ideally suited for the preparation of combination products with surface
active properties such as partial glycerides, N-acylated amino acids and sugar esters. A
common problem associated with enzymatic acylations of hydrophilic materials in
hydrophobic aprotic organic solvents is the low solubility of the above substrates in such
media. Consequently, practical solutions had to be developed in order to obtain acceptable
yields. Using a) immobilizations on solid supports, b) supersaturated solutions and c)
temporary protection groups acceptable results were achieved in most cases. In the
lecture examples for the preparation of the above product lines will be discussed, this also
in context with similar activities in other research groups.
25

L13
O-Acylated Hydroxy carboxylic acid anhydrides: Novel Building Blocks
for Surfactants and Emulsifiers
Bernd Jakob, Hans-Josef Altenbach, Manfred Schneider, Karsten Lange, Rachid Ihizane,
Zeynep Ylmaz, and Sukhendu Nandi, University of Wuppertal, Wuppertal, Germany
bjakob@uni-wuppertal.de
We recently discovered that hydroxy carboxylic acids like malic, tartaric and citric acid can
be converted in one step and quantitatively into the title compounds by reacting them with
fatty acid chlorides. The title compounds are excellent electrophiles for ring opening
reactions with a broad variety of nucleophiles – also frequently from renewable resources -
such as alcohols, carbohydrates, amines, amino acids and amino sugars. This way a wide
variety of novel surface active compounds are obtained, many of which turned out to be
interesting (useful) surfactants and/or emulsifiers for applications in cosmetics, as food
additives and for a variety of industrial processes. In the lecture we describe a) the
preparation of these materials, b) their surface active properties c) antimicrobial activities.
26

L14
Biocompatible surfactants from renewable hydrophiles
Maria Rosa Infante, Lourdes Perez, MCarmen Moran, Ramon Pons, and Aurora Pinazo,
IQAC - CSIC, Barcelona, Spain
rimste@cid.csic.es
There is today a strong trend to replace conventional surfactants with more
environmentally benign compounds. Manufacturers and consumers demand for novel
environmentally friendly surfactants from renewable resources produced by clean and
sustainable technologies (bio-based surfactants). The challenge is to find molecules which
meet mild, biodegradability, as well as performance and cost benefit requirements. The
use of hydrophilic renewable raw materials to prepare novel “natural” surfactants is an
exciting and attractive research activity to conciliate the sustainable issues with the
industrial development. In this talk we will describe significant advances have been made
in the field of surfactants derived from hydrophilic sources: lysine and arginine.
27

L15
28
Gemini-Tensides and Ion Channels from Fatty acids
Markus Dierker and Hans J. Schäfer, Organisch-Chemisches Institut der Universität
Münster, Münster, Germany
schafeh@uni-muenster.de
Nature provides in fatty acids a raw material of high synthetic value. Fatty acids are even
numbered carboxylic acids with 12 to 24 carbon atoms and an unbranched alkyl chain that
bears one to several - mostly Z-configurated - double bonds and hydroxy groups in
distinct positions.
A variety of efficient synthetic conversions has been reported for fatty acids [1]. These
comprise C,C-bond formations and functional group interconversions. There are
substitutions of CH-bonds in ω- and ω-1-position, in allylic position or adjacent to a
carbonyl group. Described are furthermore electrophilic, radical, nucleophilic additions,
cycloadditions, metathesis, formation of triple bonds and their conversion. Carbon atoms
adjacent to the carboxyl group can be subjected to radical coupling and addition by way of
electrochemical decarboxylation.
Higher value products have been obtained by us by combining the amphiphilic nature of
the fatty acid with bioactive groups [2], carbohydrates [3], dyes [4], corrosion inhibitors [4],
antioxidants [5] and as organogels [6] or ion channels [7].
Tensides are surface active compounds for which the amphiphilic nature of fatty acids
provides excellent preconditions. For applications of domestic oils as tensides the
hydrophilic properties of C18 to C22 fatty acids have to be increased. We report here on
Gemini-tensides obtained by attaching two polar groups to the double bond of oleic acid,
erucic acid and petroselinic acid [8]. Polar groups are ethoxylates, carbohydrates, sulfates
and phosphates.
The tensidic properties of the compounds as water solubility, decrease of the surface
tension, critical micelle concentration, interfacial tension and foaming behaviour are
reported and compared with these from lauric oils.
The 9,10-bis(methylethyleneglycol) adduct to methyl oleate turned out to be an artificial ion
channel. The activity was determined by measurements of the acid induced fluorescence
decay in vesicles and ion conductance of single channels in lipid membranes. The ion
conductivity is comparable to this of the natural ion channel forming compound:
gramicidine. As gramicidine the synthetic channels exhibit an antibiotic acitivtity against
Gram-positive and Gram-negative microorganisms.
[1] U. Biermann, W. Friedt, S. Lang, W. Lühs, G. Machmüller, J. O. Metzger, M. Rüsch
gen. Klaas, H.J. Schäfer, M.P. Schneider, Angew. Chem. 2000, 29, 2206.
[2] C. Kalk, Dissertation, Universität Münster 2001.
[3] A. Weiper, H.J. Schäfer, Angew. Chem. 1990, 29, 195
[4] G. Feldmann, H. J. Schäfer, Oleagineux Corps gras Lipides 2001, 8, 60.
[5] C. Kalk, H. J. Schäfer, Oleagineux Corps gras Lipides 2001, 8, 89.
[6] K. Dreger, Dissertation, Universität Münster, 2004.
[7] T. Renkes, H. J. Schäfer, P. M. Siemens, E. Neumann, Angew. Chem. 2000, 39, 2512.
[8] M. Dierker, Dissertation, Universität Münster 2000.

L16
Aliphatic ß-Chlorovinylaldehydes as versatile building blocks in
syntheses of heterocycles
Annett Fuchs, Dieter Greif, and Melanie Kellermann, University of Applied Sciences,
Zittau, Germany
a.fuchs@hs-zigr.de
Aliphatic ß-chlorovinylaldehydes are readily prepared from alkyl methyl ketones using
Vilsmeier-Haack-Arnold reaction.
Alkyl
O
CH 3
DMF/POCl 3
A survey of the literature often shows complex reactions by great expending time and
resources for getting aliphatic substituted heterocycles. On the other hand such
compounds can easily synthesize from ß-chlorovinylaldehydes by reaction with O-, N- and
S-nucleophiles. So we synthesized a variety of heterocyclic systems like isothiazoles,
pyrazoles, quinolines, isoxazoles, thiophenes and pyrimidines.
H 3C
Alkyl
S
N
N
EtO
O
Alkyl
CH 3
S
Alkyl
CH 3
Alkyl
H 3C
N
Alkyl
H2N N CH3 A survey of the literature let us expect that these compounds have a broad spectrum of
useful biologically activity. With this research we look for new applications of fatty
renewable materials in the matter of fine chemicals. It is also of interest that aliphatic ß
chlorovinylaldehydes show a different reaction behavior compared with those described in
the literature.
CHO
Cl
Alkyl
Cl
CHO
Alkyl
CH 3
H 3C
Alkyl
H 3C
H 3C
Alkyl
Alkyl
O
N
N
N
Ph
N
H
O
CH 3
N
N
29

L17
30
Calendula Oil as Paint Additive
Ursula Biermann (a), Werner Butte (a), Ralf Holtgrefe (b), Willi Feder (b), and Jürgen O.
Metzger (a), (a) University of Oldenburg, Oldenburg, Germany, (b) bio pin, Jever,
Germany; ursula.biermann@uni-oldenburg.de
During the last few years modern synthetic methods have been applied extensively to fatty
compounds for the selective functionalization of the C,C-double bond of unsaturated fatty
compounds and gave a large number of novel fatty compounds from which interesting
properties are expected.[1] Presently our interest is focused to plant oils containing
unsaturated fatty acids with a highly reactive hexatriene system such as calendula oil and
tung oil. The latter – obtained from the nuts of the tung oil tree - is a drying oil and is used
for a number of products including varnish, resins, inks, paints and coatings. Similar
properties are expected from calendula oil. Octadec-8,10-trans-12-cis-trienoic acid
(calendic acid) is the main fatty acid (ca. 60%) in the seed oil of calendula officinalis. We
obtained calendic acid esters from the native oil by a simple transesterification method
using alcohols, i.e. methanol, ethanol or isopropanol and sodium methoxide as catalyst.
The solvent-free Diels-Alder reaction of methyl calendulate and maleic anhydride gave
exclusively one highly functionalized cycloaddition product in 78% yield. The endo-8,12cycloaddition
product was formed with high regio- and stereoselectivity.[2] The reaction
can be applied to the native oil as well.
In a patent by DSM methyl calendulate is described as a very efficient reactive diluent.[3]
In addition to this we obtained even better results for ethyl and isopropyl calendulate as
reactive diluent showing low viscosity and good drying properties.
In special applications e.g. in coating material used in the outskirt area the substitution of
tung oil should be possible by calendula oil.
[1] U. Biermann, W. Friedt, S. Lang, W. Lühs, G. Machmüller, J.O. Metzger, M. Rüsch gen.
Klaas, H.J. Schäfer, M.P. Schneider, Angew. Chem., 2000, 112, 2292-2310, Angew.
Chem. Int. Ed. 2000, 39, 2206-2224.
[2] U. Biermann, W. Butte, T. Eren, D. Haase, J. O. Metzger, "Diels–Alder Reactions with
Conjugated Triene Fatty Acid Esters", Eur. J. Org. Chem., 2007, 3859–3862.
[3] Z. Theodorus, DSM NV (NL): EP0685543, 1995.

L18
Crops: A Green Approach toward Self-Assembled Soft Materials
George John, City College of City University of New York,
New York, USA
john@sci.ccny.cuny.edu
This talk presents novel and emerging concept of generating various forms of soft
materials from renewable resources. In future research, developing soft nanomaterials
from renewable resources (an alternative feedstock) would be fascinating yet demanding
practice, which will have direct impact on industrial applications, and economically viable
alternatives. Our continuous efforts in this area led us to develop new glycolipids from
industrial byproducts such as cashew-nut-shell-liquid, which upon self-assembly produced
soft nanoarchitectures including lipid nanotubes, twisted/helical nanofibers, low-molecularweight
gels and liquid crystals. More recently, we have developed multiple systems based
on biobased organic synthesis by chemical/biocatalytic methods for functional
applications. We used the ‘chiral pool’ of carbohydrates using the selectivity of enzyme
catalysis yield amphiphilic products from biobased feedstock including amygdalin,
trehalose and vitamin-C. Amygdalin amphiphiles showed unique gelation behaviour in a
broad range of solvents such as non-polar hexanes to polar aqueous solutions.
Importantly, an enzyme triggered drug-delivery model for hydrophobic drugs was
demonstrated by using these supramolecularly assembled hydrogels. Intriguingly, by
combining biocatalysis, with principles of green and supramolecular chemistry, we
developed building blocks-to-assembled materials. Also address the advances that have
led to the understanding of chiral behaviour and the subsequent ability to control the
structure of glycolipid nanostructures, and the resulting impact of this on future material
applications. These results will lead to efficient molecular design of supramolecular
architectures and nanomaterials from underutilized plant/crop-based renewable
feedstocks.
Related References:
1. Vemula, P., John. G. Crops: A Green Approach toward Self-Assembled Soft Materials. Accounts of
Chemical Research 41, 769-782, (2008).
2. Vemula, P., Douglas, K., Achong, C., Kumar, A., Ajayan, P., John. G. Autoxidation Induced Metal
Nanoparticles Synthesis in Biobased Polymeric Systems: A Sustainable Approach in Hybrid Materials
Development. Journal of Biobased Materials and Bioenergy 2, 218-222 (2008).
3. Kumar, A., Vemula, P., Ajayan, P. M., John, G. Silver Nanoparticles Embedded Anti-microbial Paints
Based on Vegetable Oil. Nature Materials 7, 236-241 (2008).
4. John, G., Vemula, P. Design and Development of Soft nanomaterials from Biobased Amphiphiles. Soft
Matter 2, 909-914 (2006). Front cover page feature.
5. Vemula, P., Li, J, John, G. Enzyme Catalysis: Tool to Make and Break Amygdalin Hydrogelators from
Renewable Resources - A Delivery Model for Hydrophobic Drugs. Journal of American Chemical Society
128, 8932-8938 (2006). Highlighted in Green Chemistry 8, 675 (2006).
6. John, G., Zhu, G., Li, J., Dordick J. S. Enzymatically-Derived Sugar Containing Self-Assembled
Organogels with Nanostructured Morphologies. Angewandte Chemie International Edition 45, 4772-4775
(2006). Front cover page feature. Angewandte Chemie 118, 4890-4893 (2006).
7. John, G.; Masuda, M.; Jung, J., H; Yoshida, K.; Shimizu, T. “Unsaturation Influenced Gelation of Aryl
Glycolipids” Langmuir, 2004, 20, 2060-2065.
8. John, G., Minamikawa, H., Masuda, M. and Shimizu, T. “Liquid Crystalline Cardanyl Glucopyranosides”
Liquid Crystals, 2003, 30, 747.
9. John, G.; Jung, J. H.; Shimizu, T. “Morphological Control of Helical Solid Bilayers in High-Axial-Ratio
Nanostructures through Binary Self-assembly”. Chem. Eur. J. 2002, 8(23), 5494-5500.
10. John, G.; Masuda, M.; Shimizu, T. “Nanotube Formation from Renewable Resources via Coiled
Nanofibers” Adv. Mater. 2001. 13 (10), 715-718.
31

L19
32
Exploiting vegetable oils for the delivery of hydrophilic drugs
Sarina Grinberg, Charles Linder, and Eliahu Heldman, Ben-Gurion University of the
Negev, Beer-Sheva, Israel
sarina@bgu.ac.il
The use of oils and fats as pharmaceuticals dates back to biblical times. Through the ages,
the science and technology of fats and oils and their chemical derivatives has progressed
from traditional products to high-value applications, including lipid-based drug delivery
systems. Lipid-based drug delivery is considered a viable strategy for increasing drug
efficacy and reducing drug toxicity. Liposomes are among the lipid-based delivery systems
which are extensively studied but targeting them to specific tissues, is still problematic.
Toward overcoming the limitations of the classical liposomes (made of phospholipids that
form bilayer membrane), we are developing lipid-based monolayer cationic vesicles made
of bolaamphiphilic compounds containing two hydrophilic head groups at each end of an
alkyl chain. The concept is to mimic the high chemical and physical stability of
archaebacteria membranes, which is made from bolaamphiphiles. Since it is hard to
isolate bolaamphiphiles from araebacteria and their synthesis is also difficult, we took a
different approach - synthesizing novel bolaamphiphiles designed to form stable nano
vesicles from functional vegetable oils that are excellent renewable resources for the
chemical industry. Vernonia oil, a naturally epoxidized triglyceride obtained from the seeds
of Vernonia galamensis, is probably the most promising of these functional oils with
respect of a facile synthesis of functionalized bolaamphiphiles. Yet, other natural fatty
acids, or oleochemicals derived from them, can also serve as a starting material for the
synthesis of such bolaamphiphiles.
Here we describe the synthesis of a series of symmetrical and asymmetrical
bola¬amphiphilic compounds that form vesicles with unique properties needed for targeted
drug delivery. When the head groups are substrates for an enzyme with high activity at the
target tissue, the vesicular structure will be disrupted and the vesicles will release the
encapsulated drug primarily there. Conjugates between vernonia moiety and polyethylene
glycol (PEG) or chitosan, were also prepared and incorporated into the membrane of the
cationic vesicles in order to prolonged the circulatory survival of the vesicles and to
increase penetrability through the blood-brain barrier (BBB) and the intestinal wall.
Efficacy of these vesicles as a drug delivery system was demonstrated with encapsulated
enkephalin (ENK) that was shown to induce analgesia whereas non-encapsulated ENK did
not cause any analgesic effect.
In summary, we have demonstrated that cationic vesicles with monolayer membrane
made from novel bolaamphiphiles with head groups that are hydrolyzed by specific
enzyme with high activity at the target tissue constitute an efficient targeted drug delivery
system.

L20
The role of renewable resources for Bayer Material Science
Ralf Weberskirch, Bayer Materials Science, Leverkusen, Germany
ralf.weberskirch@bayerbms.com
The usage of renewable resources has a long tradition in chemical industry. Depletion of
fossil resources, climate change and CO2 footprint discussions along with technical
breakthroughs in the past decade to convert renewable resources more efficiently have led
to many initiatives in industry and academia as well as to further explore opportunities of
renewable resources. [1]
In this presentation an overview will be given how BayerMaterialScience approaches the
area of renewable resources and two examples will be discussed in more detail relating to
the polyurethane industry: (1) The use of vegetable oils for the manufacture of polyetherpolyols
with a renewable content ranging from 40-70 % by weight and (2) the use of
succinic acid in polyester-polyols and as a C4 platform chemical. [2]
References:
[1] http://www.nachwachsende-rohstoffe.de/
[2] Bayer research, Ausgabe 20, p.16 – 20; „Gründe Kunststoffe“ als Ersatz für die
Erdölchemie.
33

L21
34
VEGETABLE OIL-BASED TRIOLS FROM HYDROFORMYLATED FATTY
ACIDS AND POLYURETHANE ELASTOMERS
Zoran S. Petrović, Ivana Cvetković, DooPyo Hong, Xianmei Wan
Kansas Polymer Research Center, Pittsburg State University, Pittsburg, KS 66762
and
Wei Zhang, Timothy Abraham, Jeffrey Malsam
Cargill Inc, Minnetonka, MN 55391
zpetrovi@pittstate.edu
Novel bio-based polyols were prepared from hydroformylated oleic acid (9-hydroxymethyloctadecanoic
acid) methyl esters and trimethylol propane by transesterification.
Hydroformylation produces primary hydroxyls, which allow relatively lower
transesterification temperatures and better yields than hydroxyfatty acids with secondary
OH groups. These non-crystallizing polyols (HFME) have no double bonds and their
viscosities are acceptable. Polyurethane elastomers prepared by reacting these polyols
with diphenylmethane diisocyanate (MDI) had glass transitions temperatures from -33 to -
56 o C, depending on the molecular weight of the triols. Tensile strength and Shore A
hardness were higher and elongation, swelling and sol fraction lower than those of
corresponding networks from polyricinoleic polyols. The plasticizing effect of longer
dangling chains in HFME-based polyurethanes were matched to a certain degree by the
presence of double bonds in the polyricinoleic polyols, effectively resulting in similar glass
transitions.

L22
New approaches to polymers and composites from plant oils
Selim Küsefoglu, Bogazici University Chemistry Department, Istanbul, Turkey
kusef@boun.edu.tr
Almost all commercially successful polymers and plastics are now synthesized from
petroleum based raw materials. Manufacture of useful polymers from plant oils would
present a number of advantages such as the renewability of the raw materials, fast
biodegradability of the polymers and cheaper prices. Synthesis of polymers from plant oils
is not new: ancient Egyptians used flax oil to protect the wood in their ships. However
synthesis of rigid, load bearing polymers that are suitable for fiber reinforcement is a new
and very active research field.
When an organic chemist looks at a triglyceride the double bonds, the allylic
positions, the carbonyl group and the alfa position to the carbonyl group are noticed as the
only useful positions for derivatization. So the task of the polymer chemist is to synthesize
new monomers from plant oils using these functional groups. The following are some
examples from our efforts in this field.
Epoxidation of the soybean oil double bonds followed by opening of the epoxy ring
with acrylic acid gave acrylated epoxidized soybean oil (AESO) which is a plant oil based
analog of vinyl ester resins. When this monomer is mixed with styrene reactive diluent, a
liquid molding resin is obtained which can be reinforced with glass fiber and can be cured
free radically to give laminates with a tensile strength of 450Mpa (1)
O
O
O
O
O
O
O
O
O
O
O
O
ESO
AESO
COOH
O
O
OH
O
Plant oils can be brominated at the allylic positions easily . Reaction of allylic bromide with
silver isocyanate gives the isocyanate substituted triglyceride. This molecule can be easily
converted to polyurethanes with various diols and polyols and particularly, with hydroxyl
bearing oils such as castor oil. Thus the first example of a polyurethane where both of the
monomers are plant oil based are obtained. The polymer is suitable for the production of
flexible foams. (2)
Acrylated epoxidized soybean oil can be reacted with furylamine in a Michael reaction.
When the amine is the limiting reagent a desired fraction of the acrylate groups can be
preserved for future manipulations. The resulting amine can be easily quaternized with
methyl iodide and the product turns out to be an excellent exfoliating agent for
montmorillonite clay. XRD analysis indicated an increase in intergallery distance from 12
O
O
O
O
O
O
O
O
O
O
O
O
Br
Alilik Bromine SO
AgNCO in THF
R.T.
NCO
Isosiyanatlanmis SO
35

A to 26 A. When a sample of exfoliated clay is mixed with AESO and free radically cured
one observes a 30 % increase in modulus with a 2 % clay loading. This constitutes the first
nanoclay reinforced material whose matrix polymer and exfoliating agent are plant oil
based. (3)
Our work in this exciting field has so far produced approximately 140 new plant oil based
polymers among which 12 are promising in terms of mechanical properties and ease of
synthesis. Newer strategies wherby the oil based monomer is grafted onto an existing high
molecular weight polymer are now being persued with the hope of increasing fracture
toughness of the products.
References:
1. US Pat. 6.121.398 S.Kusefoglu, R.Wool
2. S.Kusefoglu, G.Caylı, J.Applied Pol. Sci., 109, 2948 (2008)
3. E.Altuntas, G.Çaylı, N.Nugay, S.Kusefoglu, Designed Mon.and Poly. ,11, 371 (2008)
36
O
O
O
O
O
O
O
O
O
O
O
O
AESO
1-)
H2N O
furfuryl amine
FQAESO
O
2-) CH 3I / K2CO3
O
OH
OH
O
O
I + N
O

L23
Vegetable-oil based thermosetting polymers
Marina Galià, Joan Carles Ronda, Gerard Lligadas, Virginia Cádiz, University
Rovira i Virgili Tarragona, Spain
marina.galia@urv.cat
In the search for sustainable chemistry, there are increasing demands for replacing
petroleum derived raw materials with renewable raw materials in the production of
polymers. The importance of natural products for industrial applications becomes very
clear from a social, environmental and energy standpoint, with the increasing emphasis on
issues concerning waste disposal and depletion of non renewable resources. Vegetable
oils are one of the cheapest and most abundant, annually renewable natural resources
available in large quantities from various oilseeds and are now being used in an increasing
number of industrial applications. In recent years, extensive work has been done to
develop polymers from triglycerides of fatty acids as the main component.
The purpose of our research is to develop new biobased thermosetting polymers from
vegetable oils as renewable resources. Vegetable oils are triglycerides of different fatty
acids with varying degrees of unsaturation. Although they possess double bonds, it is
generally considered difficult to polymerise vegetable oils themselves due to its low
reactivity. Our research focuses on improving the physical properties of triglyceride based
materials, because they demonstrated low molecular weights and light crosslinking,
incapable of displaying the necessary rigidity and strength required for structural
applications by themselves. In this way, polymers ranging from soft rubbers to hard
plastics can be obtained by cationic copolymerisation with styrene and divinylbenzene.
Like other organic polymeric materials, the flammability of vegetable oil based materials is
a shortcoming in some applications. The concept of sustainable development requires fire
retardant technologies to be developed which have minimum impact on health and the
environment through the life cycle of the fire-retardant material; that is to say, its synthesis,
fabrication, use, recycling and disposal. To further extend the application of renewable
resources and to obtain flame retardant polymers, we synthesized polymers from
vegetable oils, styrene, divinylbenzene and silicon, phosphorus or boron-containing
reactive modifiers.
The presence of double bonds makes possible to attach some functional groups through
chemical modification and we described various chemical pathways for functionalising
triglycerides and fatty acids. An enone-containing triglyceride was obtained by an
environmentally friendly chemical procedure from high oleic sunflower oil that could be an
interesting alternative to epoxidized vegetable oils to produce thermosets by crosslinking
with conventional aromatic diamines. In a similar way, triglycerides containing secondary
allylic alcohols can be obtained, that can be further functionalised with acrylate or
phosphorus-containing derivatives to obtain flame retardant themosets. We also obtained
organic-inorganic hybrid materials with promising properties for optical applications by the
hydrosilylation of alkenyl-terminated fatty acid derivatives and biobased polyhedral
oligomeric silsesquioxanes-nanocomposites. Moreover, we described the preparation of a
new family of epoxidized methyl oleate-based polyether polyols which were used in the
synthesis of polyurethanes with specific applications: silicon-containing polyurethanes with
enhanced flame-retardant properties and polyurethane networks with potential applications
in biomedicine.
37

L24
38
Chemo-enzymatic synthesis of oil polyols and polyurethanes of them
Tomas Vlcek, SYNPO, Pardubice, Czech Republic
tomas.vlcek@synpo.cz
In this work we have studied possibility to apply chemo-enzymatic catalysis for preparation
of new types of oil polyols. Starting raw materials were methylesters of
hydroxyfunctionalized fatty acids derived from castor oil, hydroformylated soybean oil, and
epoxidized soybean oil ring opened with low molecular weight (poly)alcohols. Reacting
these fatty acids with green growing centers such as 1.3-propanediol or glycerol we were
able to synthesize 100 % renewable content polyols differing in molecular weight, and
hydroxyl group’s functionality. We catalyzed the condensation reactions with up to 5 wt. %
of immobilized Candida antarctica lipase B (Novozym 435). Setting up the reaction
temperature to 70 °C and applying low pressure we allowed easy removal of a side
product, methanol. Curing the synthesized oil polyols with aliphatic and aromatic type of
isocyanate we prepared model polyurethane cast resins and evaluated physicalmechanical
properties of these materials. We will discuss results of our work in our
presentation.

L25
Study of ASA (alkenyl succinic anhydrides) from fatty acid esters of
vegetable oils as paper sizing agents
Laure Candy, Carlos Vaca-Garcia, Elisabeth Borredon, Laboratoire de Chimie
AgroIndustrielle; ENSIACET, Toulouse, France
laure.candy@ensiacet.fr
New sizing agents from natural origin were obtained by reaction between maleic anhydride
and esters from vegetable oils and mainly alkyl oleates. They belong to the alkenyl
succinic anhydrides family (ASA).
Paper hydrophobation, which limits water penetration, relies upon the reaction between
the hydroxyl fonctions of cellulose and the anhydride moiety of ASA.
Our vegetable ASA (oleo-ASA) are characterized by a maximum composition in C18:1 and
a varying terminal ester moiety. More than thirty oleo-ASA were tested as paper sizing
agents at laboratory scale. Among them, three oleo-ASA presented a sizing and an
emulsion behaviour equivalent to the one obtained with petrochemical ASA, commonly
used in industry. Moreover, their hydrolysis in diacid is two-fold slower and their resistance
to stripping phenomenon is ten-fold higher. Their use would then allow longer emulsion
storage and fewer deposits in air ducts.
These advantages make them excellent candidates to the substitution of ASA from fossil
origin. Once the synthesis and purification of the three preceding molecules optimized, one
among them has been successfully tested as sizing agent at a 100 kg paper machine pilot
scale.
Acknowledgements: Authors wish to thank ONIDOL and ADEME for their financial
support.
39

L26
40
Use of vegetable oil based thermosetting resins in compound stone
Technology
Stefano Zeggio, and Fabio Bassetto, Breton Research Centre, Castello di Godego, Italy
zeggio.stefano@breton.it
Unsaturated orthopthalic polyester resins (hereafter indicated as UP resins), dissolved in
styrene, are widely used as binders to aggregate stone and other inorganic raw materials
in the production of compound stone slabs using vibratory compaction in a vacuum
environment, patented worldwide as Bretonstone Technology.
The use of UP resins involves some technical inconveniences: both resin and styrene
monomer are oil-based, hence they come from non-renewable sources and their cost
mainly depends on the value of crude oil; due to its high volatility rate, styrene is a
dangerous chemical, which involves the designing of complex and expensive intake and
burning plants.
Many efforts are dedicated to the development of a new organic binder, having similar
properties to those of UP resins, which may solve these difficulties.
We have found that chemically modified vegetable oil could be used as new renewable
raw material: the epoxidation of vegetable oils with a high iodine number (such as soybean
and linseed oil) forms epoxidated oils which are cured with aliphatic dicarboxilic anhydride,
preferably in liquid state. The curing process must be accelerated using a basic catalyst.
The new resin contains more than 50% by weight of renewable raw materials and contains
no volatile organic components.
The properties of both new thermosetting resin and compound stones produced in this
way are even better than traditional ones. In fact, the mechanical properties (such as the
flexural strength and the water absorption) and the aesthetic effect (valuated technically by
the gloss value) of the industrial slab remain constant, but the resistance to weather
conditions (evaluated by QUV panel) is increased. The latter feature permits the use of
compound stone in many outdoor applications.

L27
Life cycle assessment of high performance polyamides
Georg Oenbrink, Martin Roos, Franz-Erich Baumann, Harald Häger, Evonik Degussa
GmbH, Marl, Germany, harald.haeger@evonik.com
Introduction
Although fossil carbon sources make up less than 10% of all materials utilised, there is
currently intensive discussion in the chemical industry on the use of renewable raw
materials to produce fine chemicals and also monomers for polymer production.
In Brazil, for instance, Braskem and DOW are planning to produce ethylene and then
polyethylene from sugarcane-based ethanol. This is just one example of recent attempts to
produce known basic petrochemical materials from renewable raw materials.
The approach is somewhat controversial, however, because the starting compound,
sucrose, has a carbon to oxygen ratio of 1:1, while the target polyethylene molecule is a
pure hydrocarbon. Even assuming maximum theoretical yields, more than three metric
tons of sugar are required to produce one metric ton of polyethylene.
On the other hand, synthetic routes based on renewable raw materials to produce basic
chemicals had been used industrially for many years, until such plants became
uneconomical with the advent of highly cost-effective cracked products from fossil carbon
sources. The research effort required for a return to the earlier approach would therefore
be fairly small. The slight technological risk exists, however, that it might not be possible to
build up the relevant patent portfolio.
In another approach, “new” monomers are produced from renewable raw materials. An
example is provided by DuPont's biotechnologically produced 1,3-propanediol. In
polyesters such as Sorona and Hytrel, this diol produces materials with new properties.
Patent protection for substances and applications is undoubtedly possible here. However,
new materials must be entered in the relevant registers of chemicals and launched on the
market.
Application-oriented characterisation and market launch of new materials cannot be
delayed until the new biotechnological production methods for the relevant monomers
become available. A production plant for these monomers must therefore be built, at least
on a pilot scale, which allows their synthesis by "classical" chemical methods.
41

Polyamides from Renewable Raw Materials
Polyamides are a class of materials of which representatives based on renewable raw
materials have been known for at least 50 years. Most of these are based on castor oil and
its cracked product ricinoleic acid methyl ester.
Boiling with NaOH produces sebacic acid. According to Arnold and Smolinsky 1) , pyrolytic
cracking at temperatures above 500°C produces 10-undecylenic acid, which is converted
in further reaction steps to 11-amino carboxylic acid and PA11. Other representatives of
the class of polyamides based on renewable raw materials are PA610 and PA1010, both
of which are based on sebacic acid.
In the above processes, significant amounts of by-products and waste are unavoidably
produced.
This is why, in the 1970s, polyamides were developed from petrochemical raw materials,
which process generates significantly less waste. PA12 is a typical example of such
compounds.
Polyamides from Renewable Raw Materials—Back to the Future?
Following the rapid growth of petrochemical-based polyamides during the final decades of
the last century, there has been increased interest over the last few years in sustainable
products, resulting in intensified marketing of fatty-acid based polyamides as
biopolyamides.
At the K’2007, BASF announced the re-introduction of PA610 and DuPont of PA1010. For
the last couple of years, Arkema has been advertising its own PA11 as a biopolyamide.
It must be pointed out, however, that the underlying synthetic methods will continue to be
based on the above mentioned chemistry, with high proportions of by-products and waste.
Polyamides from renewable raw materials therefore continue to offer promise for the
future: The task that lies ahead is to combine the sustainability of renewable raw materials
with the sustainability and selectivity of petrochemical production methods.
In this talk we will discuss and compare the various production methods for polyamides.
Property profiles of polyamides from renewable raw materials and of their petrochemical
analogues will be discussed. First results from a life cycle assessment of different
polyamides will be discussed as well. Finally, suggestions will be proposed as to how the
sustainability of the resources can be combined with “green” chemistry.
1) R.T. Arnold, G. Smolinsky J. A. C. S. 81, 6443, 1959, J. Org. Chem. 25, 129, 1960
42

Abstracts
Part 2: Posters
43

P1
Catalytic cleavage of methyl oleate or oleic acid
A. Köckritz 1 , M. Blumenstein 2 , A. Martin 1
1
Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Branch Berlin, 12489 Berlin
2
Hobum Oleochemicals GmbH, 21047 Hamburg; angela.koeckritz@catalysis.de
Introduction
The cleavage of oleic acid via ozonolysis is the industrially applied process for the
synthesis of azelaic acid from renewables. Alternatives are in demand due to safety
concerns of ozone handling. Recently the authors reported on the epoxidation of methyl
oleate with molecular oxygen in the presence of aldehydes. 1 Now the cleavage of oleic
acid or methyl oleate using this system and additionally OsO4 or potassium osmate as
catalysts is presented.
Experimental
In a typical experiment, 2 mmol substrate, 7.5 mmol aldehyde, 0.04 mmol OsO4 or
K2OsO4�2H2O and 50 mg azobisisobutyronitrile were placed in a 100 ml Buechi glass
autoclave and were dissolved in 20 ml of the appropriate solvent. Then the autoclave was
pressurized with 4 bar O2 and stirred at 70-90°C for 1-4 hours. The progress of the
reaction was controlled by GC-MS.
Results
Monomethyl azelate 4 (R=CH3) and pelargonic acid 5 were the main products in the Oscatalyzed
oxidation of methyl oleate 1 (R=CH3) with O2/aldehyde besides varying amounts
of the epoxide 2 and the diol 3, whereas azelaic acid (4, R=H) was solely obtained from
oleic acid (1, R=H). However, a comparative application of RuO4 or RuO2 instead of Oscatalysts
did not lead to cleavage products.
The simultaneous formation of the cleavage products 4 and 5 as well as of the epoxide 2
and the diol 3 is interpreted mechanistically as parallel reactions (route A-C), this
assumption was supported by monitoring the course of reaction. Epoxide 2 seems to be
evolved according both to a radicalic and non-radicalic pathway. The formation of 2 in 42%
yield by oxidation of methyl oleate in the presence of 2,6-di-tert.-butyl-4-methyl-phenol
argues for a non-radicalic mechanism, probably peracid is generated from the aldehyde
via Os-catalysis. A further conversion of 2 under these conditions did not lead to 3 but only
to a minor degree to 9- or 10-keto derivatives.
44

A
H3C (CH2) 7 CH CH
1
(CH2) 7 COOR
O
H3C (CH2) 7 CH
2
CH (CH2) 7 COOCH3 H3C(CH2) 7 COOH + HOOC (CH2) 7 COOR
B
4 5
OH
H3C (CH2) 7 CH CH (CH2) 7 COOCH3 OH
3
C
R=CH 3,H
Fig. 1. C=C cleavage of oleic acid or methyl oleate
The diol 3 originated supposably by direct Os-catalyzed dihydroxylation of 1 using in situformed
peracid. This guess was drawn on the increase in yield of 3, if the reaction
conditions were adapted to known optimal dihydroxylation conditions (e.g. addition of
diazabicyclooctane, solvent DMF or MeCN/H2O/ethyl acetate). A possible acid-catalyzed
cleavage of 2 to 3 or of 3 to 4 and 5 was found to a minor degree. The direct cleavage of
the double bond of 1 to 4 and 5, most likely via a glycolate complex, was also presumed to
be non-radicalic due to significant amounts of products, even under application of a radical
scavenger. Also in that case, the reaction of O2 with the aldehyde to peracid is likely. On
the basis of the experimental results, the reaction pathways B and C to 4 and 5, discussed
in Figure 1, seem not to be the preferred routes at least. In summary, the obtained yields
of 5 (R=CH3) amounted to 50-70%. Suitable solvents were acetone or dichloromethane,
more polar or aqueous-organic mixtures decreased the yield.
If oleic acid was used as substrate under equal reaction conditions, surprisingly only the
formation of 4 and 5 in about 50 % yield (non-optimized) was observed.
The authors gratefully acknowledge the Federal Ministry of Education and Research
(BMBF) for financial support (FKZ 22003704).
1 A. Köckritz, M. Blumenstein, A. Martin, Eur. J. Lipid Sci. Technol. 110, 581-586 (2008)
45

P2
46
Heterogeneously catalyzed hydrogen-free deoxygenation
of saturated C8, C12 and C18 carboxylic acids
S. Mohite, U. Armbruster, M. Richter, D.L. Hoang, A. Martin
Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Außenstelle Berlin,
Richard-Willstätter-Str. 12, 12489 Berlin; andreas.martin@catalysis.de
Biodiesel comprises fatty acid methyl esters with various chain lengths. It has clear
environmental advantages compared to fossil fuels, nevertheless, some drawbacks rise
from its limited shelf life, corrosion in vehicle engines, and lower energy value. These are
mainly related to oxygen content of biodiesel, which should be removed. Possible ways for
upgrading are pyrolysis [1] or hydrogenation [2,3]. In presence of H2 and noble metal
catalysts (Pd, Ru, Ni) the latter route selectively forms hydrocarbons. Though H2 addition
leads to high yields of desired paraffins, the use of external H2 sources lowers process
economy. A hydrogen-free route may benefit from decomposition of by-product glycerol
that generates H2 in situ. This work focused on model studies to investigate the hydrogenfree
deoxygenation of C8, C12, and C18 acids exclusively.
Supported Ni and Pd catalysts (1-10 wt-%) were prepared by impregnation of ZrO2, active
carbon, zeolites, and hydrotalcites. Autoclaves (25 ml) served for catalytic tests. Catalysts
were reduced in situ with H2 (300 °C, 2 h) and the vessel was flushed with N2. Then,
solutions of carboxylic acids in dodecane or tetralin were added and the reaction was
started.
Initial catalyst survey was done with lauric acid (C12) at 300 °C. With supported Ni
catalysts, highest conversion was found on 10%Ni/ZrO2 (59 %) and 5%Ni/ZrO2 (57 %), but
alkane selectivity was little. In a second series, Pd catalysts supported on active carbon
were tested. The best performing catalyst was 10%Pd/C with 37 % undecane yield at 68
% conversion of lauric acid. Such Pd catalysts then were used for deoxygenation of
caprylic acid (C8) and stearic acid (C18). At similar reaction conditions (300 °C, 6 h), chain
length of carboxylic acid has a strong impact on conversion as well as alkane selectivity
(caprylic acid: X = 35 %, S = 54 %; lauric acid: X = 55 %, S = 68 %, stearic acid: X = 93 %,
S = 13 %). The observed maximum in selectivity may be due to increased cracking as a
side reaction, the probability of which increases with number of carbon atoms and bonds.
At 300 °C, conversion without H2 addition may not be favorable for long chain carboxylic
acids anymore.
Further work aimed at optimization of reaction conditions with 10%Pd/C catalyst. Raising
temperature also was found to have a strong promotional effect on carboxylic acid
conversion as well as alkane selectivity. Increasing pressure lowered conversion, but
improved selectivity towards alkane. Characterization of spent catalyst 10%Pd/C showed a
slight loss in Pd content due to leaching, but no agglomeration of metal particles.
[1] D.G. Lima et al., J. Anal. Appl. Pyrolysis 71 (2004) 987.
[2] I. Kubickova et al., Catal. Today 106 (2005) 197.
[3] http://www.nesteoil.com/default.asp?path=1,41,539,7516,7522

P3
Flame retardant polyesters from renewable resources via ADMET
Lucas Montero de Espinosa, Joan Carles Ronda, Virginia Cádiz, Universitat Rovira i
Virgili, Tarragona, Spain, and Michael A. R. Meier, University of Applied Sciences
OOW, Emden, Germany; lucas.montero@urv.cat
Polyesters are widely used for textile fibers, technical fibers, films, bottles or as a finish on
high-quality wood products. The demand of polyesters in 2006 is an estimated 35 million
tons and will grow annually by 9%.[1] Due to environmental concerns much work is
devoted to the industrial use of products from renewable resources, and for this reason the
development of polymeric materials, such as polyesters, from renewable resources has
attracted much attention.[2] On the other hand, many kinds of flame retardants (FRs) have
been tested to improve the flame retardancy of polyesters and have been applied to
commercial products. Among these, phosphorous FR and halogenated FR are the most
common. However, many kinds of halogenated FR, especially brominated FR, are
restricted in many countries due to the formation of dioxin under combustion. Therefore
most of the inherent FR polyesters are now produced using phosphorous FR by blending
and/or copolymerizing with flame retardants. However, to obtain efficient flame retardancy
by blending, high amounts of the flame retardant agent must be added and usually the
polymer properties are affected. Also, when a blended fiber is washed, the blended flame
retardants migrate to the fiber surface, leading to decreased flame retardancy and
increased danger for the customers. Because of these problems, the copolymerizing
method is becoming more common.
Acyclic diene metathesis polymerization (ADMET) has been shown to be an efficient tool
for the synthesis of a wide variety of polymers and polymer architectures that are not
available using other polymerization methods.[3] Among them, polyesters can be prepared
with molecular weights that range between 20.000 and 70.000. In the present work, a
renewable phosphorus containing monomer bearing two 10-undecenoic acid moieties has
been homopolymerized and copolymerized with a 10-undecenoic acid derived monomer[4]
via ADMET using the Grubbs second generation metathesis catalyst. Polymers with Mn up
to 65.000 were obtained in absence of solvent. This procedure allowed us to synthesize a
variety of polyesters with controlled phosphorus contents which are promising candidates
for flame retardant materials.
1. Yang, S. C.; Kim, J. P. J App Polym Sci, 2007, 106, 2870–2874
2. Meier, M. A. R.; Metzger, J. O.; Schubert, U. S. Chem Soc Rev, 2007, 36, 1788–1802
3. Schwendeman, J. E.; Church, A. C.; Wagener, K. B. Adv Synth Catal, 2002, 344, 597-
613
4. Rybak, A; Meier, M. A. R. ChemSusChem 2008, 1, 542-547
47

P4
48
Catalytic access to bifunctional products from plant oil derivatives
Xiaowei Miao, C. Fischmeister, C. Bruneau, P. H. Dixneuf, Institut Sciences
Chimiques de Rennes, Rennes, France; mxw331@yahoo.com
Plant oils constitute a class of renewable raw materials which can produce a large variety
of chemicals useful for industry. The cross-metathesis of unsaturated fatty esters, derived
from seed oils, with functionalized olefins has potential to generate bifunctional
compounds, as it has been shown by reactions with acrylates[1]. The objective of our
presentation will be to describe, with some practical aspects, the cross-metathesis
reactions of both terminal and internal double bond containing esters, arising from seed
oils, with acrylonitrile. This metathesis was performed using ruthenium catalysts and led to
bifunctional nitrile-esters with high conversions [2]. TON improvement was achieved by
slow addition of catalyst.
It will be shown that the metathesis catalyst residue can be used as a hydrogenation
catalyst in a sequential cross-metathesis/hydrogenation process leading to saturated
nitrile-esters.
The prepared bifunctional nitrile-esters are precursors of amino acid monomers for the
production of polyamides from renewable resources.
[1] A. Rybak, M. A. R. Meier, Green Chem., 2007, 9, 1356; Green Chem., 2008, 10, 1099.
[2] For initial study see: R. Malacea, C. Fischmeister, C. Bruneau, J-L. Dubois, J-L.
Couturier, P. H. Dixneuf, Green Chem., 2009, in press.

P5
Synthesis and Characterization of Surfactants from Renewable Resources
Rachid Ihizane, Bernd Jakob, Karsten Lange, Zeyneb Yilmaz, Sukhendu Nandi,
Manfred P. Schneider and Hans. J. Altenbach , Fachbereich C – Mathematik und
Naturwissenschaft, Fachgruppe Chemie, Bergische Universität Wuppertal,
Wuppertal, Germany; Email: ihizane@uni-wuppertal.de
The conversion of fatty acid with natural hydroxycarboxylic acids, especially malic-,
tartaric- and citric acid resulted in the easy formation of acylated hydroxycarboxylic
anhydrides. We have shown that this class of anhydrides provides convenient entry into a
variety of products. They readily react with natural or synthetic nucleophiles like alcohols,
carbohydrates, amines and amino acids. A series of compounds were synthesized and
characterized, their surface and antibacterial properties have been measured.
49

P6
Synthesis of bifunctional monomers via homometathesis of fatty acid Derivatives
50
Jürgen Pettrak, Herbert Riepl, Martin Faulstich, and Wolfgang A. Herrmann, TU
München, Lehrstuhl für Rohstoff und Energietechnologie, Straubing, Germany;
juergen.pettrak@wzw.tum.de
Thermoplastic elastomers consist of two molecular regions, an amorphous region for
elastic and a harder crystalline section for thermoplastic properties. Long-chained
bifunctional compounds, products of the conversion of fatty acids, can serve as “soft”,
amorphous monomer. The synthesis of bifunctional monomers from oleic acid and their
derivatives for the production of polymers based on renewable resources is thus useful in
the field of thermoplastic elastomers.
Organo-metal-catalyzed metathesis [1] of C18-compounds, based on oleic acid [2], oleic
acid esters [3, 4] and other readily available educts from the tenside industry such as oleyl
alcohol [5], oleic amide and amines as feedstock can supply the necessary bifunctional
monomers for polycondensation. The metathesis of oleic acid provides two olefins,
octadec-9-ene and octadec-9-ene-1,18-dicarboxylic acid, both C18 compounds. The
homometathesis of oleic acid and derivatives -functionalized fatty�,�therefore is an
interesting way to synthesize acid compounds.
To be applied later in industry, the production of these monomers must be scaled up now.
Ruthenium compounds for metathesis belong to a class of extremely efficient catalysts,
tolerant to many functional groups. Technical grade educts may provide catalyst poisoning
effects. Especially nitrogen-containing compounds present many problems due to their
basicity. We report the metathetic synthesis of bifunctional products, based on nitrogen
based derivatives. Ruthenium-based homometathesis of oleic acid esters, oleyl alcohol,
oleic acid amides and oleyl amines have been conducted. For esters and oleyl alcohol,
maximum conversion could be achieved, even with technical grade educts without further
pretreatment. Even solvent-free synthesis at low catalyst loadings was possible. The C18diester
was obtained via thin film evaporation, the diol was obtained via precipitation and
recrystallization.
Oleyl amine itself could not be converted, but protected amines, like oleyl amides or oleyl
n-alkyl-amines can be converted. The metathetical conversion of amides provide a lower
yield in bifunctional compounds compared to diester and diol, but is nevertheless
interesting, because the diamide precipitates during reaction and is easily isolized via
centrifugation and recrystallization.
References:
1. Grubbs, R.H., Handbook of Metathesis, ed. R.H. Grubbs. Vol. 1-3. 2003, Weinheim: Wiley-CH. 204.
2. Foglia, T.A., H.L. Ngo, and K. Jones, Metathesis of unsaturated fatty acids: Synthesis of long-chain
unsaturated-alpha,omega-dicarboxylic acids. Journal of the American Oil Chemists Society, 2006. 83(7): p.
629-634.
3. Boelhouwer, C. and J.C. Mol, Metathesis Reactions of Fatty-Acid Esters. Progress in Lipid Research,
1985. 24(3): p. 243-267.
4. Van Dam, P.B., C. Boelhouwer, and M.C. Mittelmeijer, Metathesis of Unsaturated Fatty-Acid Esters by a
Homogeneous Tungsten Hexachloride-Tetramethyltin Catalyst. Journal of the Chemical Society-Chemical
Communications, 1972(22): p. 1221-1222.
5. Brändli, C. and T.R. Ward, Libraries via Metathesis of Internal Olefins. Helvetica Chimica Acta, 1998.
81(9): p. 1616-1621.

P7
Synthesis and evaluation of value added products from Glycerol
Avinash Bhadani, and Sukhprit Singh, Guru Nanak Dev University, Department of
Chemistry, Amritsar, India; avinashbhadani2003@yahoo.co.in
The use of renewable feedstock like Glycerol for producing important industrial chemicals
having bulk demand is the priority of 21st century. Glycerol is an important by product of
biodiesel manufacturing which is produced by transesterfication during the production of
biodiesel fuel. Approximatly 10 kg of glycerol is produced for every 100 kg of oil taken for
production of biodiesel. With the total production of biodiesel in thousands of tons, huge
amount of glycerol is also produced as a by product. 1 It has been estimated that by 2010
the overall production of glycerol will touch 1.2 million tons. The cost of B100 type
biodiesel can be reduced from US$ 0.63 to US$ 0.35 provided the use of glycerol is
enhanced for the production of value added products.2 In spite of green origin and over
production the scientific community had not been able to fully explore potential usefulness
of this naturally occurring molecule for making value added products.
Recently our research group reported synthesis of β-Bromo Glycerol Monoethers directly
from α-Olefins by cohalogenation protocol.3 With the continuation of our work we have
developed glycerol based pyridinium surfactants and compared its properties with some
commercially available surfactants. We found better surface and biological properties such
as low cytotoxicity towards animal cell line and better DNA binding capability of new
glycerol based cationic surfactants. As the production of cationic surfactants amounts to
350000-500000 tones per annum.4 The replacement of commercially available cationic
surfactants with new glycerol based surfactants will check loss of energy and resources
due to over production of glycerol.
Literature
1. Pagliaro, M.; Rossi, M. The Future of Glycerol. RSC Green Chemistry Book Series.
2008.
2. Zhou, Chun-Hui.; Beltramini, J. N.; Fan, Yong-Xian and Lu, G. Q. Chemoselective
catalytic conversion of glycerol as a biorenewable source to value commodity chemicals.
Chem. Soc. Rev. 2008, 37, 527-549.
3. Singh, S.; Bhadani, A.; Kamboj, R. Synthesis of β-Bromo glycerol monoethers from αolefins.
Ind. Eng. Chem. Res. 2008, 47, 8090-8094.
4. Gunstone, F.D.; Padley, F. B. Lipid Technologies and Application. CRC Press Book,
1997.
51

P8
New Polymers from Plant Oil Derivatives and Styrene-Maleic Anhydride Copolymers
52
Cem Öztürk, and Selim Küsefoğlu, Bogazici University, Chemistry Department,
Istanbul, Turkey ozturkce@boun.edu.tr
*
O O O
X=2 Y=1
*
n=8
Styrene-Maleic Anhydride Copolymer
SMA2000
(Ratio Styrene-MaleicAnhydride 2:1 )
+
+
O
O
O
O
O
O
H 3CO
O
EMO (Epoksidized Methyl Oleate)
O
O
O
O
O
ESO (Epoxidized Soy Oil )
*
*
H 3CO
HO
O
OH
X=2
O
HO
O
X=2
O
SMA-EMO
OH
*
Y=1
O
OH
-O Y=1
O
O
HO
X=2
O
O -
SMA-ESO
O
Y=1
*
O O
O O
O
O
*
Y=1
O
n=8
Polymerization of triglycerides is usually carried out by attaching a polymerizable group to
the triglyceride [1]. Polymers derived from such monomers have low connectivity and low
mechanical properties due to the bulky structure of the monomer. This manifests itself in
low fracture toughness of the polymers obtained. In this work we changed our strategy by
starting first with a suitably substituted polymer having a reasonable molecular weight and
attaching the triglyceride derivative to it. This strategy is bound to provide molecular
weights that are higher and provide the entanglement lengths needed for higher fracture
toughness.
In this study, styrene maleic anhydride copolymer (SMA2000, Styrene:Maleic Anhydride
2:1) is grafted and/or crosslinked with epoxidized methyl oleate, epoxidized soybean oil,
methyl ricinoleate, castor oil and soybean oil diglyceride. Base catalyzed epoxy-anhydride
and alcohol-anhydride reactions were carried out by using the anhydride on SMA, the
epoxy or secondary alcohol groups on the triglyceride based monomers. The
characterizations of the products were done by DMA, TGA and IR spectroscopy. SMAepoxidized
soy oil and SMA-castor oil polymers are crosslinked rigid infusible polymers.
SMA-epoxidized soy oil and SMA2000-castor oil showed Tg’s at 70 and 66 ºC
respectively. Dynamic moduli of the two polymers were 11.73 and 3.34 Mpa respectively.
SMA-epoxidized methyl oleate, SMA-methyl ricinoleate and SMA-soy oil diglyceride
polymers were soluble and thermoplastic polymers and were characterized by TGA, GPC,
DSC, NMR and IR spectroscopy.
References:
[1]. Rios, L. A., Ph.D. Thesis, Rheinisch-Westfälischen Technischen Hochschule, Aachen,
2003.
*
X=2

P9
Chain Extension Reactions of Unsaturated Polyesters with Epoxidized Soybean Oil
Ediz Taylan, and Selim Küsefoglu, Bogazici University, Chemistry Department,
Istanbul, Turkey; etaylan@boun.edu.tr
Unsaturated polyesters were chain extended with epoxidized soybean oil. The molecular
weight increase was monitored using Gel Permeation Chromatography. The obtained
polymer was characterized by FTIR and 1H-NMR, styrene solubility and gel time. The
chain extended polyester was then diluted with styrene and cured with a radical initiator
and compared to a commercial reference polyester. Thermal and mechanical properties of
the cured polyester were characterized by DMA and TGA. The results show that
unsaturated polyesters can be chain extended with epoxidized soybean oil which
substantially shortens the condensation polymerization during manufacture, without
compromising their thermal and mechanical properties.
53

P10
Soybean Oil Based Isocyanates: Synthesis, Characterizations and Polymerizations
54
Gökhan Çaylı, and Selim Küsefoğlu, Bogazici University, Chemistry Department,
Istanbul, Turkey; gcayli@ku.edu.tr
Isocyanates are valuable compounds that are used widely in many application areas of
polymer industry. The most important area of use of isocyanates is to synthesize
polyurethanes and polyureas. Important isocyanates, used in the polyurethane
manufacturing, are 2, 4-toluene diisocyanate (2,4TDI), 2, 6-toluene diisocyanate (2,6TDI),
4, 4’-diphenyl methane diisocyanate (MDI), 1, 6 hexamethyl diisocyanate (HMDI), xylene
diisocyanate (XDI), and isophorone diisocyanate (IPDI), all of which are petroleum derived
[1-3].
Isocyanates can be synthesized in many ways. The Curtius, Hoffman and Lossen
rearrangements, which may involve nitrene as an intermediate, are not succesful for large
scale operations [4].
Literature search reveals a number of bio-based polyurethanes. In almost all of them,
castor oil was used as a polyol source and petroleum based isocyanates were used as the
isocyanate [5-12]. There are no examples where the isocyanate is bio-based. With the
simple synthesis described in this work it is possible to obtain polyurethanes where both
the isocyanate and polyol are bio-based.
In the first strategy, soybean oil isocyanates were obtained by substitution reaction
between allylically brominated soybean oil and AgNCO [13]. In the second strategy,
soybean oil was reacted with iodine isocyanate reagent [14-15]. Addition of iodo
isocyanate to plant oils gives valuable intermediates. Similar to thiocyanogen addition, just
one mole iodo isocyanate can be added to one mol of polyunsaturated fatty acids. This
means that one mole unsaturated plant oil triglyceride can bind around three mol iodo
isocyanate easily. Many positional isomers are obtained at the end of the both reaction.
The products are valuable intermediates to synthesize poly-urethanes and poly ureas.
Synthesized soybean oil isocyanate and iodo isocyanate were polymerized with castor oil
and glycerol. Castor oil and glycerol polyurethane of soybean oil iodo isocyanate showed
tensile strength of 140 KPa and 270 KPa respectively. On the other side, polyurethanes of
soybean oil isocyanate with same triols showed tensile strength of 100 and 125 KPa
respectively
References
1. Dwan’isa, J.-P. L.; Mohanty, A. K.; Misra, M.; Drzal, L. T. In Natural Fibers, Biopolymers and
Biocomposites; Mohanty, A.K.; Misra, M.; Drzal, L. T., Eds.; CRC: Boca Raton, FL, 2005; Chapter 25.
2. Dhimiter Bello, D.; Woskie, S. R.; Streicher, R. P.; YouchengLiu, Y.; Stowe, M. H.; Eisen, E. A.;
Ellenbecker, M. J.; Sparer,J.; Youngs, F.; Cullen, M. R.; Redlich, C. A. Am J Ind Med 2004, 46, 480.
3. Schmelzer, H. G.; Mafoti, R. M.; Sanders, J.; Slack, W. E. J Prakt Chem 1994, 336, 483. 4. Hepburn, C.
Polyurethane Elastomers; Elsevier Applied Science: London, 1992.
5. Traˆn, N. B.; Jean Vialle, J.; Pham, Q. T. Polymer 1997, 38, 2467.
6. Lligadas, G.; Ronda, J. C.; Galia`, M.; Ca´diz, V. Biomacromolecules 2006, 7, 2420.
7. Barikani, M.; Mohammadi, M. Carbohydr Polym 2007, 68, 773.
8. Dwan’isa, J.-P. L.; Mohanty, A. K.; Misra, M.; Drzal, L. T.; Kazemizedah, M. J Mater Sci 2004, 39, 1887.
9. Lligadas, G.; Ronda, J. C.; Galia´ , M.; Biermann, U.; Metzger, J. O. J Polym Sci Part A: Polym Chem
2006, 44, 634.
10. Hatakeyemaa, H.; Tanamachi, N.; Matsumura, H.; Hirose, S.; Hatakeyamab, T. Thermochim Acta 2005,
431, 155.
11. Rheineck, A. E.; Shulman, S. Fett/Lipid 70, 239.
12. Marwan, R. K.; Don, E. F. U.S. Pat. 3,481,774 (1968).
13. Cayli, G.; Kusefoğlu, S; J. App. Pol. Sci. 2008, 109, 2948.
14. Hassner, A.; Heathcock, C.C.; Tetrahedron Letters, 1964, 19/20, 1125.
15. Metzger, J.O.; Fuermeier, S., European Journal of Organic Chemistry, 1999, 3,661.

P11
Aliphatic ß-chlorovinylaldehydes as versatile building blocks in syntheses of
Heterocycles
Annett Fuchs, Dieter Greif, and Melanie Kellermann, University of Applied Siences,
Zittau, Germany; a.fuchs@hs-zigr.de
Aliphatic ß-chlorovinylaldehydes are readily prepared from alkyl methyl ketones using
Vilsmeier-Haack-Arnold reaction.
Alkyl
O
CH 3
DMF/POCl 3
Alkyl
Cl
CHO
A survey of the literature often shows complex reactions by great expending time and
resources for getting aliphatic substituted heterocycles. On the other hand such
compounds can easily synthesize from ß-chlorovinylaldehydes by reaction with O-, N- and
S-nucleophiles. So we synthesized a variety of heterocyclic systems like isothiazoles,
pyrazoles, quinolines, isoxazoles, thiophenes and pyrimidines.
H 3C
Alkyl
S
N
N
EtO
O
Alkyl
CH 3
S
Alkyl
CH 3
Alkyl
H 3C
N
H2N N CH3 A survey of the literature let us expect that these compounds have a broad spectrum of
useful biologically activity. It is of interest that aliphatic ß-chlorovinylaldehydes show a
different reaction behavior compared with those described in the literature. In this poster
we will report experimental details on syntheses and spectroscopic studies of the
described compounds.
CHO
Cl
Alkyl
Alkyl
H 3C
Alkyl
H 3C
H 3C
Alkyl
Alkyl
O
CH 3
N
N
N
Ph
O
N
H
CH 3
N
N
55

P12
Syntheses and reaction behavior of long-chained alkyl methyl ketones starting from
fatty acids, fatty alcohols and fatty nitriles
56
M. Kellermann, A. Fuchs, D. Greif, University of Applied Sciences, Zittau, Germany
m.kellermann@hs-zigr.de
There are well known a lot of methods for preparation of fatty ketones. Long-chained alkyl
methyl ketones can also prepared from different fatty compounds using the following
reactions.
H 3C
O
R COOH
COOEt
CH 3Li
H3C COOH + R Li
R
O
R CN
OLi
+
+
+
R CH 2Br
H 3C MgX R
OMgX
CH 3
OLi
H 3C
H 3C R
O
H3C MgI
CH3CN route A R CH3route B
O
O
O
H 3C R
H 2O/H +
O
R
R CH 3
MgBr
We investigated the synthesis of long-chained alkyl methyl ketones systematically in order
to optimize reaction conditions, yields and purity of the products.
We also report in this poster about new applications of the microwave technology to
transform fatty acids derivatives and fatty alcohols into long-chained alkyl methyl ketones.
These compounds are versatile building blocks to synthesize long-chained substituted ßchlorocrotonaldehydes.
R
O
CH 3
DMF/POCl 3
R
Cl
CHO
CH 3
R
(A)
(B)
(C)
(D)
(E)

P13
Hydrophobic modification of Inulin in aqueous media using alkyl epoxides and
basic catalysis
Jordi Morros, Bart Levecke, and Mª Rosa Infante, IQAC - CSIC, Barcelona, Spain
jmcste@cid.csic.es
Inulin, the polydisperse reserve polysaccharide from chicory, has been modified with fatty
epoxy derivatives of different chain length in high alkaline aqueous media. Etherification of
inulin has been carried out with high efficiency. The influence of several reaction
parameters such as amount of organic co-solvent, catalysts, reaction time and
temperature has been studied. After purification, emulsion power of the final products was
tested, considering these products as promising green polymeric surfactants.
57

P14
58
Short Chain Sugar Amphiphiles: Alternative Oil Structuring Agents
Swapnil R Jadhav, Praveen Kumar Vemula, and George John, City College of City
University of New York, New York, USA; Jadhav sjadhav@gc.cuny.edu
Owing to the need of developing environmentally benign functional materials by adopting
green chemistry methods, usage of biorefinery concept for the development of biobased
molecular building blocks of such materials has emerged as a prime focus of the current
research. The present study focus of developing sugar based low molecular weight gels (a
type of functional soft materials) by enzyme catalysis exemplifies the above approach. The
underexplored open chain sugars (sugar alcohols) were chosen as hydrophilic moieties to
develop low molecular weight gelators (LMWGs). Mannitol, sorbitol and xylitol were
selected as representative sugar alcohols (headgroups) and series of amphiphiles were
synthesized by attaching hydrophobic carboxylic acids at one-end of the sugar using an
enzyme-mediated regioselective transesterification reaction. For control tuning of
hydrophobicity various carboxylic acids different chain length were attached (typically
(CH2)4-14). The resulting amphiphiles were studied for their self-assembling behavior in
organic liquids. Only the amphiphiles with short chains {(CH2)4-8} were found to be
efficient organogelators; immobilizing various solvents ranging from crude oil fractions to
vegetable oils. In addition, Effect of chiral and structural variations in sugar amphiphiles on
microstructure formation (responsible for immobilization of organic liquid) was also
investigated in detail. Furthermore, the efficiency of the short chain sugar amphiphiles as a
healthy alternative structuring agents for vegetable oils compared to existing oil structuring
agents was studied and has been demonstrated in this report.

P15
Novel enzymes for lipid modification
H. Brundiek, R. Kourist, M. Bertram, and U. Bornscheuer, University of Greifswald,
Greifswald, Germany; henrike.brundiek@uni-greifswald.de
Enzymes have received considerable and increasing attention in lipid modification over the
last few years. In particular, hydrolases have a high potential for applications such as the
lipases-catalyzed interestification [1, 2] as an alternative for the hydrogenation of fats or
the preparation of designer-fats [3].
Many enzymes, however, do not fulfill all demands of a technical process. Properties such
as stability under process conditions or the chemical selectivity leave often much to
improve. Together with this growing demand for tailor-made lipases goes the increasing
knowledge about the molecular structures. Considerable progress in molecular biology
techniques has made the cloning and expression of lipases in bacteria and the subsequent
improvement by techniques of state-of-the art protein design [4] possible.
An alternative for the improvement of enzymes by protein design represents the screening
for novel enzymes. The limited number of commercially available lipases can be extended
by high-throughput screening in enzyme collections. Enzymes from metagenome
represent a rich source for this purpose.
Herein we present an outline and the scope of both techniques that can provide novel
biocatalysts for new applications in lipid-modification.
______________________________________
[1] Bornscheuer U. und Kazlauskas R., 2005: Hydrolases in Organic Synthesis, Regio-
and Stereoselective Biotransformations. Monographie, Wiley-VCH, Weinheim. ISBN-10: 3-
527-31029-0,ISBN-13: 978-3-527-31029-6
[2] Bornscheuer U., Adamczak M, Soumanou M. M., 2002: Lipase-catalyzed synthesis of
modified lipids. In: Lipids as constituents of functional foods . Bridgwater, 149-182
[3] Soumanou M., 1997: Lipase-catalyzed synthesis of structured triglycerides containing
medium-chain fatty acids in sn1 and sn3-position and a long-chain fatty acid in sn2position.
Stuttgart, Univ., Diss.
[4] Bornscheuer U., Lutz, S. (Eds.), 2008: Protein Engineering Handbook. Wiley-VCH,
Weinheim. ISBN-10: 352731850X, ISBN-13: 9783527318506
59

P16
Production of fine and bulk chemicals using silage as a renewable resource
60
Tim Sieker, and Roland Ulber, University of Kaiserslautern, Kaiserslautern,
Germany; tim.sieker@mv.uni-kl.de
The presented work aims for the use of silage as a renewable resource for the
fermentative production of bulk- and fine chemicals and is a cooperation with the Institute
of Thermal Process Engineering at the University of Kaiserslautern and the Institute of
Biochemical Engineering at the Saarland University.
In 2006 321,300 ha of farmland were used for the production of grass and clover, yielding
36,268,000 t of harvested grass clip. Thus, grass clip provides an enormous potential as
renewable resource in Germany. Since fresh grass clip is available only during summer
and it decays if stored inappropriately, it is conserved by ensiling.
In the ensiling process, the water-soluble carbohydrates are fermented to lactic acid,
resulting in a pH-shift and thus the conservation of the silage. The processes in
development are to use the remaining carbohydrates, including cellulose and
hemicellulose, as well as the lactic acid produced during ensiling. Aspired products are
ethanol, 1,2-propanediole, itaconic and succinic acid. Remnants and wastes of the
processes should be reuseable as animal food or in biogas production, resulting in a
complete substantial and energetic utilisation of the silage.
In the presented work two strategies for the utilization of silage are pursued:
First, a silage juice containing the water-soluble carbohydrates and the lactic acid is won
directly from the silage by pressing. This silage juice can either be used directly as a
cultivation medium or by the isolation of the contained lactic acid, the main product of
ensiling, and its further use.
Secondly, the hydrolysis of the celluloses and hemicelluloses contained in the silage is
aspired. After the separation of solid and liquid phases the latter, a mixture of organic
acids produced during ensiling and pentoses and hexoses released during hydrolysis, is
fermented.
Taken together the described work is able to offer an all-season renewable resource for
the production of base and fine chemicals and to increase the value of an agricultural
product respectively to improve the economics of biogas production.
The Project is funded by the Fachagentur für Nachwachsende Rohstoffe (22025407
(07NR254)).

P17
Enzymatic degradation of pre-treated wood
Sebastian Poth, Magaly Monzon, Nils Tippkötter, and Roland Ulber, University of
Kaiserslautern, Germany; poth@mv.uni-kl.de
The economic dependency on fossil fuels and the changes of climate due to them has led
to an intensive search for renewable resources for the production of chemicals and fuels.
At present there are several processes established which use sugar cane and corn for the
production of bioethanol. As these crops are commonly used as food there is an ethical
drive to use alternative resources for industrial processes. Promising feedstock for the
chemical and fuel production are in this context the fermentable sugars derived from
wooden celluloses and hemicelluloses by enzymatic hydrolysis. The great challenge in this
regard is to design new simple and beneficial processes that can compete against
conventional petrochemical production processes.
The most important step in these processes is the hydrolysis of the lignocellulosic material
into the corresponding sugar monomers, which can be fermented to ethanol for example.
The aim of the presented work is to optimize the enzymatic hydrolysis with regard to the
used substrates and the usage of hydrolysates for the fermentation of alcohol. The
substrates are cellulose and hemicellulose fractions obtained by thermo-chemical pretreatment
of beech wood. This pre-treatment is carried out by our project partner at the
Johann Heinrich von Thünen Institute, Hamburg, Germany.
Several commercially available enzymes, even thermo stable ones were tested on their
ability to degrade these fractions. In first experiments it could be shown, that the enzymes
can hydrolyse up to 40 % of the cellulosic fraction into fermentable sugars within 24 h. The
hemicellulosic fraction already contains some monomeric sugars which can be fermented.
For this fraction the use of hemicellulases is investigated. All sugar containing
hydrolysates and fractions were tested for their suitability as carbon source for a cofermentation
of two different yeasts to produce ethanol. The results showed that the
addition of a nitrogen source, vitamins and trace-elements is the only necessary
preliminary step for the fermentation. To increase the yield of sugars in the hydrolysates
further optimizations were made, e.g. the increase of substrate concentration and the
amount of added enzymes was investigated.
61

P18
62
PA X,20 from renewable resources via metathesis and catalytic amidation
Hatice Mutlu,and Michael A.R. Meier, University of Applied Sciences OOW, Emden,
Germany; hatice.mutlu@fh-oow.de
Polyamides (PA) are engineering plastics with various commercial applications due to their
outstanding properties such as high durability, high hardness and rigidity [1]. Methods for
the production of polyamides by polycondensation of aliphatic diamines and dicarboxylic
acids or the polyaddition of lactams are often described in the literature. These articles are
mostly dedicated to standard polyamides based on depleting fossil resources. However,
bio-based polyamides are not yet well developed. The unique example of industrially
produced 100% bio-based polyamide is the AB-type polyamide-11 [2]. Synthesis of 100%
bio-based AABB type polyamides are not expected because of the non-availability of biobased
diamines. Meanwhile, research on routes to obtain diacids from glucose (adipic
acid) or vegetable oils (azelaic acid, sebacic acid) for the production of partially biobased
polyamides-6,6, -6,9, and -6,10 are under investigation [3].
Among various polycondensation methods, acyclic diene metathesis (ADMET)
polycondensation is useful in the synthesis of a veriety of polymer architecures that would
otherwise be difficult to obtain [4]. The main goal of this study is to describe the synthesis
of unsaturated polyamides that can be obtained from plant oil derivatives via two different
approaches. First, long chain aliphatic α,ω dienes with two symmetrically spaced amide
segments were polymerized via ADMET polymerization. Secondly, E-dimethyl-eicos-10enedioate,
a bio-based unsaturated monomer that was obtained via metathesis and other
reactions from castor oil, was polymerized with different aliphatic diamines using strong
organic bases, such as TBD, as catalysts. Both reaction pathways led to PA X,20 and the
two different routes were investigated, optimized and comapred to one another. Moreover,
the properties of the resulting polyamides were investigated revealing that these longchain
polyamides are well applicable as engeneering plastics and that their properties
depended on the structure of the applied monomers, as expected. Last, but not least our
investigations led to new synthetic approaches that allow for the synthesis of ABA type
polyamide block-copolymer with interesting application possibilities.
References:
1. M. I. Kohan (editor), Nylon plastics handbook. New York: Hanser, 1995.
2. M. A. R. Meier, J. O. Metzger, U. S. Schubert, Chem. Soc. Rev. 2007, 36, 1788.
3. M. Crank, M. Patel, F. Marscheider-Weidemann, J. Schleich, B. Hüsing, G. Angerer,
Techno-Economic Feasibility of Large-Scale Production of Bio-Based Polymers in Europe,
O. Wolf, Technical Report EUR 22103 EN, European Communities 2005.
4. T. W. Baughman, K. B. Wagener, Adv. Polym. Sci. 2005, 176, 1.

P19
DERIVATIVES OF VEGETABLE OILS AS COMPONENTS OF HYDRAULIC FLUIDS
Talis Paeglis, Aleksejs Smirnovs, Rasma Serzane, Maija Strele, Mara Jure, Riga
Technical University, Riga, Latvia; aleksejs86@inbox.lv
Though not total loss lubricants, hydraulic fluids have been classified as “high risk loss”
lubricants - they are used in large volumes in equipment that is susceptible to spills. The
hydraulic fluids currently used in Latvia in wood harvesting and other environmentally
sensitive areas still are mainly based on mineral oils. Completely different is situation in
other EU countries, e.g., in Sweden, where the Swedish standard SS 155434 for
biodegradable hydraulic fluids is a legal requirement. There is an obvious need for
elaboration of formulations of hydraulic fluids based on renewable natural resources in
order to initiate and to promote production of such products in Latvia.
Hydraulic fluids of harvesters should operate at temperature C and under high pressure
(180-200 atm) till�C up to 70-100�range -25 change-over after 800-1200 operating hours.
The main problems of biodegradable hydraulic fluids based on vegetable oils are their low
hydrolytic, thermal and oxidative stability, as well as bad low-temperature fluidity and shear
stability.
The biodegradable hydraulic fluids of harvesters available nowadays on market are much
more expensive than their mineral oil based analogues and often can not fulfill technical
requirements set; due to this, new and cheaper technologies are developed using
renewable base stocks. Investigations regarding new base fluids as well as new additives
are very topical.
We used rapeseed oil, its methyl- and ethylesters (RME and REE, correspondingly), byproducts
of biodiesel production - mixture of free fatty acids, mono- and diglycerides - as
raw materials for creation of biodegradable hydraulic fluids. Following basic components
for hydraulic fluids were synthesized:
• Esters of fatty acids of rapeseed oil and polyols:
o NPE - esters of neopentyl alcohol,
o TMPE - esters of trimethylolpropane,
o PEE - esters of pentaerythritol.
• Estolides of rapeseed oil and their ethylhexylesters.
Several derivatives of glycerol and fatty acids were prepared as potential additives for
improvement of technical parameters of new compositions:
• Ethers of glycerol, obtained from:
o glycerol and epoxydized rapeseed oil,
o glycerol and mixture of epoxydized rapeseed oil fatty acids and mono-, diglycerides
(formed as a by-product in biodiesel production).
• Polyhydroxycompounds, obtained from epoxydized RME.
C, as well as�C and 100�We determined kinematic viscosity at 40 viscosity index, oxidative
stability, cold-flow properties, acid value, foaming, air release, flash point of elaborated
compositions. The most of tested parameters corresponded to requirements, but low
temperature fluidity after 7 days were unsatisfactory – addition of temperature depressants
(e.g., Lubrizol 7671A) improved this parameter. We used TBHQ as oxidation inhibitor,
Lubrizol 7671A as pour point depressor and polymethylsiloxane as antifoam agent in
rapeseed oil based formulations.
63

P20
64
ULTRASOUND PROMOTED ETHANOLYSIS OF RAPESEED OIL
Pavels Karabesko, Maija Strele, Rasma Serzane, Mara Jure, Riga Technical University,
Riga, Latvia; pave23@inbox.lv
Biodiesel usually is produced by transesterification of various vegetable oils or animal fats
with methanol. Unfortunately, methanol is highly toxic and harmful to human health.
Application of bioethanol instead of methanol would lead to more environmentally friendly
production technology which almost completely would be based on renewable resources.
Currently in Europe there are no biodiesel producers using ethanol as a raw material,
nevertheless FAEE (Fatty Acid Ethyl Esters) is used as biodiesel in Brazil. Mandate to
CEN for standards for FAEE for use in diesel engines and heating fuels (M/393) was set in
2006.
Previously we explored optimization of the synthesis of rapeseed oil ethyl esters (REE)
using anhydrous ethanol and dehydrated ester-aldehyde fractions of ethanol rectification
[1]. We were interested to study possibilities of biodiesel preparation from locally produced
bioethanol. Therefore our aim was to establish optimal conditions for synthesis of
rapeseed oil ethyl esters (REE) by transesterification of oil with bioethanol produced by
distillery “Jaunpagasts Plus” from the local wheat. Experiments were carried out at room or
higher (75-80oC) temperature; duration of reaction and amount of catalyst were varied.
The best results were obtained when reaction was run 1 h at room temperature in the
presence of 1.3-1.7% KOH catalyst (from oil mass). When reaction was run at room
temperature, yield of biodiesel reached just 71-82%. Therefore we repeated the reaction,
adding catalyst-alcohol solution in two steps. The best result (yield of reaction 97%) was
reached, when total amount of added potassium hydroxide was 1.5%.
Secondly, we have established optimal conditions for production of REE using
ultrasonication, as it is well known that ultrasound assisted transesterification of fatty acids
proceed more quickly [2] allowing replacement of batch processing with continuous flow
processing and reduction of investment and operational costs. Results of our experiments
showed that duration of reaction can be reduced to 0.5 h - twice in comparison with
classical method.
Traditional workup process of REE with orthophosphoric acid and water lead to hardly
separable emulsion. Therefore we applied Magnesol for purification of REE. Biodiesel
treated with Magnesol corresponds to requirements of standard LVS EN 14214 and this
method is simpler than workup with acid and water.
We managed to prepare REE with 97% yield in two steps reaction of rapeseed oil with
bioethanol of local origin. Also we succeeded to reduce a duration of reaction by
ultrasonication (24 kHz) from 1 h to 0.5 h. Simplification of REE purification was reached
by application of Magnesol. The technical parameters of our REE corresponded to
requirements of LVS EN14214 set for biodiesel.
[1] M. Strele, R. Serzane, G. Bremers, E. Gudriniece. Investigations of oils and fats. 6.
Transesterification of rapeseed oil with ethanol. Chemistry Journal of Latvia, 1999, 4, 67-
70 (in Latvian).
[2] C. Stavarache, M. Vintoru, R. Nishimura, Y. Maeda. Fatty acids methyl esters from
vegetable oil by means of ultrasonic energy. Ultrasonic Sonochem., 2005, 12, 367-372.

P21
From Glycerine via Acetals to new Amphiphils
J. Baumgard (a,b) , E. Paetzold (a), and U. Kragl (a,b), (a) Leibniz-Institut für Katalyse an
der Universität Rostock e.V., Rostock, b) Institut für Chemie, Universität Rostock e. V.,
Rostock; jens.baumgard@catalysis.de
Bis 2010 wird die Herstellung von Biokraftstoffen aus nachwachsenden Rohstoffen
weltweit kräftig gesteigert. Natürliche Ole und Fette werden zu Biodiesel umgeestert und
bis zu 6 Millionen t Glycerin werden auf dem Weltmarkt zusätzlich erwartet [1]. Die
gegenwärtigen Anwendungsgebiete für Glycerin können diese Produktmengen nicht
aufnehmen, deshalb werden weltweit neue marktfähige Produkte auf Glycerinbasis
gesucht.[2-4]
ZIEL :
Glycerin als ein billiges Massenprodukt muss mittels chemischer Stoffwandlung in
verkaufsfähige Produkte gewandelt und auf dem Weltmarkt abgesetzt werden [2 – 4].
Ergebnisse :
Die Hydroformylierung von Olefinen führt zu Aldehyden, Aldehyde reagieren mit Glycrerin
zu Acetalen [5] (Gl. 1). Die Acetale enthalten Hydroxylgruppe, die für eine Umsetzung z.
B. mit Säure und -derivaten zur Bildung von neuartigen Amphihilen genutzt wird.
Glycerine
Gl. 1
[H + ]
Literatur:
R CO/H 2
HO
O
O
[Rh]
[1] M. Plagliaro et al Angew. Chem., 2007, 119, 45
[2] A. Behr et al. Chem. Ing. Techn., 2007, 79, 621 – 636
[3] R. Westendorf et al., Eur. Pat. Appl., 1996, 1996:501411)
[4] EP 11560242, 23.2.2006, CAO Corp.
[5] M. Beller, U. Kragl, E. Paetzold, L. Neubert, P. Kollmorgen, 2008, DE 10 2008
009 103.0
R
R
+
HO
CHO
O
O
R
65

P22
BIOBASED SEGMENTED POLYURETHANES FROM METHYL OLEATE BASED
POLYETHER POLYOLS
66
Enrique del Río, Virginia Cádiz, Marina Galià, Gerard Lligadas, Joan Carles Ronda,
Universitat Rovira i Virgili, Tarragona, Spain; enrique.delrio@urv.cat
In the polyurethane industry, conventional polyether polyols are mostly produced from
petroleum-based alkylene oxides. Due to uncertainty about the future cost of petroleum, as
well as the desire to move toward more environmentally friendly feedstocks, many recent
efforts have focused on replacing all or part of the conventional petroleum-based polyols
with those made from renewable resources such as vegetable oils. In addition, it is a
challenge to use diisocyanates derived from aminoacids, making possible to produce
polyurethanes completely from renewable resources. 1-3
In this work we report the synthesis and characterization of polyether polyols from methyl
oleate. The coordinative ring opening polymerisation of epoxidized methyl oleate yields a
linear polyether with Mn= 6.500 Da. The controlled reduction of the carboxylate groups
allows to obtain a set of polyether polyols with different primary hydroxyl contents.
Depending on the degree of reduction the polyols can have different properties and, when
converted to polyurethanes, may impart different properties to the final product.
These renewable polyols react with 4,4’-methylenebis(phenyl isocyanate) (MDI) or L-lysine
diisocyante (LDI) to yield polyurethanes with different crosslinking density. Moreover, we
carried out the reaction of the polyetherpolyol with the isocyanates and 1,3-propanediol as
chain extender to obtain segmented polyurethanes with different hard segment contains.
These materials were characterized by infrared spectroscopy (FTIR/ATR), differential
scanning calorimetry (DSC), termogravimetric analysis (TGA) thermodynamomechanical
analysis (DMTA), scanning electron microscope (SEM) and X-Ray difraction.
1 M.A.R. Meier, J.O. Metzger and U.S. Schubert, Chem. Soc. Rev., 2007, 36, 1788–1802
2 F. S. Günera, Y.Yagci, A.T. Erciyes, Prog. Polym. Sci. 31 (2006) 633–670
3 G. Lligadas, J.C. Ronda, M. Galià, V. Cádiz, Biomacromolecules, 2007, 8, 686-692

P23
DETAILED STUDIES OF SELF- AND CROSS-METATHESIS REACTIONS OF
FATTY ACID METHYL ESTERS
Guy B. Djigoue, and Michael A. R. Meier, University of Applied Sciences OOW, Emden,
Germany; djigoue@yahoo.fr
Self- and cross-metathesis[1] reactions with oleochemicals offer the potential to obtain
value added chemical intermediates from plant oil renewable resources.[2,3] Here, the
self-metathesis (SM) of methyl undec-10-enoate (1) as well as its cross-metathesis (CM)
with methyl acrylate (MA) was investigated in detail by systematically varying the applied
reaction conditions. The thus resulting unsaturated α,ω-diesters with a chainlength of 20
and 11 carbon atoms, respectively, have a large potential from the synthesis of polyesters
as well as polyamides from plant oil renewable resources.[4] Hence, four different
metathesis catalysts were investigated under solvent-free conditions at catalyst loadings
ranging from 0.1 to 1 mol % and at temperatures ranging from 30 to 70 °C. All reactions
were followed by GC and/or GC-MS in order to evaluate the conversion as well as the
selectivity of the reactions. In the case of the SM reactions good to excellent conversions
were obtained with all catalysts, but the second generation metathesis catalysts revealed
high amounts of olefin isomerisation side-reactions.[5] In general, these SM reactions were
highly reproducible, but at low catalyst loadings and low temperatures sometimes large
variations in the observed conversions were obtained. This was not the case for the
investigated CM reactions. Here, also good conversions and CM yields were observed, if
second generation metathesis catalysts were applied. Quite interestingly, these reactions
showed a better reproducibility and the olefin isomerisation of the also observed SM
products was almost completely suppressed. Moreover, due to these optimizations we
were able to run these CM reactions with a 1:1 ratio of the reactants and low catalysts
loadings, which is an improvement over described literature procedures.[3]
Thus, in summary, we report on the detailed investigation of the described SM as well as
CM reactions leading to new and optimized reaction conditions for the productions of
unsaturated α,ω-diester monomers from renewable raw materials.
References:
[1] R. H. Grubbs, Angew. Chem. Int. Ed. 2006, 45, 3760.
[2] A. Rybak, P. A. Fokou, M. A. R. Meier, Eur. J. Lipid Sci. Technol. 2008, 110, 797.
[3] A. Rybak, M. A. R. Meier, Green Chem. 2007, 9, 1356.
[4] M. A. R. Meier, J. O. Metzger, U. S. Schubert, Chem. Soc. Rev. 2007, 36, 1788.
[5] M. Arisawa, Y. Terada, K. Takahashi, M. Nakagawa, A. Nishida, Chem. Rec. 2007, 7,
238.
67

P24
Temperature dependant double bond isomerization side reactions during ADMET
polymerizations studied with a monomer from renewable resources
68
Patrice Aimé Fokou, and Michael A. R. Meier, University of Applied Sciences OOW,
Emden, Germany; atrice.fokou@fh-oow.de
Acyclic diene metathesis (ADMET) polymerization has developed into a very versatile
technique for the preparation of a variety of macromolecular architectures, including linear
polymers [1,2], polymers with a defined degree of branching [3], telechelics as well as
block-copolymers [4,5]. Recently, the technique was also applied to monomers with a
functionality > 2, thus resulting in hyperbranched macromolecules from AB2, AB3, and A3
monomers with B1 chainstoppers, respectively [6,7]. Applying this efficient catalytic
process to monomers from renewable resources will lead to the development of materials
with interesting properties that have the potential to replace existing fossil oil based
materials [8].
Within this contribution, the utilization of plant oils as renewable raw materials for
monomers and polymers will be discussed. Therefore, the synthesis of a novel and
degradable monomer from fatty acid derivatives will be described and its subsequent
ADMET polymerization discussed in detail. We will focus our discussions on the
investigation of double-bond isomerization side-reactions occurring during these ADMET
polymerizations. Therefore, the resulting polyesters were transesterified with methanol in
order to investigate the nature and the amount of isomerization side-reactions that
occurred during the polymerizations by GC-MS. These investigations revealed that the
Grubbs first generation catalyst does hardly show any side reactions up to a
polymerization temperature of 90 °C, whereas the second generation catalyst from Grubbs
showed up to 75% isomerisation side reactions depending on temperature as well as other
polymerization conditions. This study represents the first quantitative study of
isomerisation side reactions during ADMET polymerizations and will therefore help to tailor
polymeric architectures prepared via this technique.
References:
[1] P. M. O’Donnell, K. Brzezinska, D. Powell, K. B. Wagener, Macromolecules 2001, 34,
6845.
[2] T. E. Hopkins, K. B. Wagener, Macromolecules 2004, 37, 1180.
[3] J. C. Sworen, J. A. Smith, J. M. Berg, K. B. Wagener, J. Am. Chem. Soc. 2004, 126,
11238.
[4] K. R. Brzezinkska, T. J. Deming, Macromolecules 2001, 34, 4348.
[5] A. Rybak, M. A. R. Meier, ChemSusChem 2008, 1, 542.
[6] I. A. Gorodetskaya, T.-L. Choi, R. H. Grubbs, J. Am. Chem. Soc. 2007, 129, 12672.
[7] P. A. Fokou, M. A. R. Meier, Macromol. Rapid Commun. 2008, 29, 1620.
[8] M. A. R. Meier, J. O. Metzger, U. S. Schubert, Chem. Soc. Rev. 2007, 36, 1788.

P25
Reducing the Environmental Impact of Olefin Metathesis Reactions
Manuela Kniese, Michael A. R. Meier, University of Applied Sciences OOW, Emden,
Germany; manuela.kniese@gmx.de
As with most catalytic processes, olefin metathesis was discovered by accident as a result
of the study of Ziegler polymerizations with alternate metal systems.[1] The recent
development of ruthenium olefin metathesis catalysts with high activity and functional
group tolerance has expanded the scope of this reaction to synthesize organic compounds
and to form new C-C bonds.[2,3] Many variants of this very useful and versatile reaction
have been developed in the meantime including self-metathesis (SM), cross-metathesis
(CM), ring-closing metathesis (RCM), ring-opening metathesis (ROM), ROM
polymerization (ROMP) as well as acyclic diene metathesis polymerization (ADMET).[2,3]
Within this project three reactions were investigated, which were suggested by the Nobel
Prize laureate R. H. Grubbs as a useful, general and easily applicable platform for catalyst
evaluation: CM of allyl benzene with excess cis-1,4-diacetoxy-2-butene, CM of methyl
acrylate with 5 hexenyl acetate and RCM of diethyldiallyl malonate.[4] As also typically
described for other olefin metathesis reactions, these reactions were performed in the
organic solvent dichloromethane, which is toxic and environmentally unfriendly. Since the
aim of this project is to optimize the reaction conditions for these reactions and to avoid the
use of toxic solvents, we studied these reactions in detail at different concentrations in two
solvents as well as in bulk. Dichloromethane and an environmentally friendly fatty acid
derived solvent were used for comparison. Our studies clearly showed that the mentioned
reactions can be performed in bulk, thus completely avoiding organic solvents and thus
highly reducing the environmental impact of such reactions. As a very positive side effect,
the reactions in bulk usually required less catalyst and often provided better conversions
than their counterparts in organic solvent, most likely due to the higher concentration of the
reactants. Moreover, our studies also revealed that methyl esters of capric and lauric acid
are suitable non-toxic and thus environmentally friendly solvents for the investigated olefin
metathesis reactions.
References:
[1] R. H. Grubbs, Tetrahedron, 2004, 60, 7117.
[2] S. H. Hong, R. H. Grubbs, Org Lett., 2007, 9 (10), 1955.
[3] R. H. Grubbs, Angew. Chem. Int. Ed. 2006, 45, 3760.
[4] R. H. Grubbs et al, Organometallics, 2006, 25, 5740.
69

P26
An approach to renewable Nylon-11 and Nylon-12 via olefin cross-metathesis
70
Tina Jacobs, Michael A. R. Meier, University of Applied Sciences OOW, Emden,
Germany; tina.jacobs@fho-emden.de
In ages of depleting fossil reserves and increasing emission of green house gases it is
obvious that the utilization of renewable feedstocks is one necessary step towards a
sustainable development of our future. Especially plant derived oils bear a large potential
for the substitution of currently used petrochemicals, since a variety of value added
chemical intermediates can be derived from these resources in a straightforward fashion
taking full advantage of nature’s synthetic potential.
Here, new approaches for the synthesis of monomers from plant oils as renewable
resources[1] via olefin metathesis[2,3] will be discussed. In particular, the synthesis of α,ωdifunctional
chemical intermediates from renewable resources via the cross-metathesis
reaction of fatty acid methyl esters with allyl chloride is described.[4] Different ruthenium
metathesis catalysts were investigated and the reaction conditions were optimized for high
conversions in combination with high cross-metathesis selectivity. New building blocks and
chemical intermediates from fatty acid derivates were thus obtained in catalytic reactions
with low catalyst loadings under bulk conditions. Therefore, a new potential use of
renewable raw materials for the synthesis of intermediates for Nylon-11 and Nylon-12 was
demonstrated.
References:
[1] M. A. R. Meier, J. O. Metzger, U. S. Schubert, Chem. Soc. Rev. 2007, 36, 1788.
[2] R. H. Grubbs, Angew. Chem. Int. Ed. 2006, 45, 3760.
[3] A. Rybak, P. A. Fokou, M. A. R. Meier, Eur. J. Lipid Sci. Technol. 2008, 110, 797.
[4] T. Jacobs, A. Rybak, M. A. R. Meier, Appl. Catal., A 2009, 353 32.

P27
Ultrasonic assisted finishing of cellulose fiber by fatty acid amide derivatives
Mazeyar Parvinzadeh, Mohammad Shaver, and Bashir Katozian, Islamic Azad University,
Shahre rey branch, Tehran, Islamic Republic of Iran mpgconf@gmail.com
The processing of textiles to achieve a particular handle is one of the most important
aspects of finishing technology. Softeners and fatty acids improve soft handle,
smoothness, elasticity, hydrophilic, antistatic and soil release properties on textiles. Fatty
acid amide derivatives are commercial textile softeners used to improve softness of fibers
surface.
In this research, cotton fabric was used as substrate and it was first scoured with nonionic
detergent to remove any impurities. The fabric was then treated with anionic, nonionic and
cationic fatty acid amide derivative softeners in water including 15 g/l at 30ºC for 30
minutes using ultrasonic energy during treatment. The treated fabrics were then
dried/cured at 130ºC for 40 seconds. Some of the physical properties of the fabrics treated
under ultrasound and those treated without ultrasonic energy, were compared and
discussed.
As the results show, treatment of fabrics with softeners under ultrasound is more effective
compared to conventional method.
71

P28
72
Hydrolysis of nylon 6 with proteolytic enzyme
Mazeyar Parvinzadeh, Islamic Azad University, Shahre rey branch, Tehran, Islamic
Republic of Iran; mpgconf@gmail.com
Nowadays, textile processing based on biotechnology has gained importance in view of
stringent environmental and industrial safety conditions. The best established application
of biotechnology to textiles is the use of enzymes. These vital parts of all living organisms
are organic catalysts with specific in the reaction catalyzed and substrates selectivity.
Traditional chemical treatments are replaced by enzymes because of their lower product
quality, higher manufacturing cost, affecting some favorable bulk properties of textiles, not
easily controlling, creating harsh conditions, undesirable side effects and/or waste disposal
problems, more waste, high odor process for workers and added energy consumption in
textile industry. The main enzymes used in textile processing are amylases, cellulases,
proteases, esterases, nitrilases, catalases, peroxidases, laccases and pectin-degrading
enzymes.
Nylon 6 fabrics were first treated with different concentrations of subtilisin enzyme in
aqueous solutions containing 1, 2, 4 and 6% for 80 min at 30ºC. The dyeing process was
then carried out on the treated fabrics with disperse dye. A UV–Vis. spectrophotometer
was used for determination of dyebath exhaustion. Disperse dye showed higher
exhaustion on the enzyme treated samples. The intensity of major peaks in FTIR spectra
of protease treated samples are in favor of chemical changes of the polypeptide fabric.
The results of color measurement in the CIELAB system showed that the darkness of the
samples increased with an increase in the enzyme percentage in the solution. The wash
and light fastness properties of samples were measured according to ISO 105-CO5 and
Daylight ISO 105-BO1 and discussed.

P29
Comparing finishing of polyester fibers with micro and nano emulsion silicones
Mazeyar Parvinzadeh, Islamic Azad University, Shahre rey branch, Tehran, Islamic
Republic of Iran; mpgconf@gmail.com
The processing of textiles to achieve a particular handle is one of the most important
aspects of finishing technology. Softeners are one of the main compounds in finishing
process and can improve some properties of textiles, depending on the chemical nature,
including soft handle, smoothness, elasticity, hydrophilic, antistatic and soil release
properties. They are classified according to their ionic character and the main classes are:
anionic, cationic, nonionic, amphoteric, reactive and silicone. Macro- and micro-emulsion
silicone softeners are commercial classes of softeners but nano-emulsions are new class
of softeners in textile industry. The purpose of this research was to study the effect of
micro and nano-silicone softeners on different properties of polyester fiber.
Polyester fabrics were first scoured with nonionic detergent and were then treated with
three concentrations (10, 20 and 30 gr/lit) of micro and nano-emulsions of silicones. The
drape length of treated samples with 10 gr/lit of solution was decreased and more
decrease was observed with increase in silicone concentration. Colorimetric properties of
softener treated fabrics were evaluated with a reflectance spectrophotometer. Nanoemulsion
silicones changed a little the surface reflectance of fibers compared to microsilicone
softener. Increase in weight of all samples was observed which shows the coating
of silicones on fiber surface. Nano-emulsion silicones showed better results on samples
treated compared to micro-emulsion silicones.
73

P30
PIBOLEO project: Eco Innovative process for multi-functional bi-oleothermal
treatment for wood preservation and fire proofing
74
Sandra Warren, Carine Alfos, and Frédéric Simon, ITERG, Pessac, France
s.warren@iterg.com
Although they are usually quite effective, typical wood treatments are not necessarily very
environment-friendly, in terms of the treatment itself and of the active substances used
(flame retardants, biocides). In this day and age, as the ecological aspects are becoming
more and more important, many research projects aim at improving wood treatment in an
environment-friendly manner.
In France a simple bi-oleothermal© process has been developed by CIRAD and FCBA in
order to make the treated wood more stable and less sensitive when used outdoors. The
interest of this now well mastered alternative method for wood protection is to allow wood
drying as well as wood treatment in a single process. This two stage process operates at
atmospheric pressure and uses two hot oil baths. Nevertheless, the formulation of the oils
used needs major improvement in order to adapt the performances of the treated wooden
material (durability towards wood destroying organisms, fireproofing, etc...) to its end-use.
The improvement of this bi-oleothermal wood treatment is the subject of the PIBOLEO
project, which is supported by the French National Agency for Research (ANR - ADEME).
This project is currently in its early stages and focuses for now on the optimization of the
composition of the second bath, which is the one containing the active substances.
The nature of the second bath depends a lot on the active substances used for improving
the fire, fungus or insect resistance of the treated wood. If these substances are not
miscible with oil but soluble in water, it is then necessary to develop an emulsion
containing enough of each of the substances to impart the desired properties to the treated
wood. In that case, the use of surfactants is required. Therefore, a major axis of the
PIBOLEO has been to optimize the surfactant systems in these water-in-oil (W/O)
emulsions. It is quite challenging to design emulsions that can withstand the thermal
shocks and the addition of impurities coming from the wood (water, sap, etc.) associated
with the treatment without dephasing.
In the case of active substances that are not soluble in oil, chemical modification and
grafting of those substances onto oil can be an alternative option. They can then become
soluble in oil without losing their properties as fire retardants or biocides. Several synthesis
routes are currently under investigation in the PIBOLEO project. In that case or if the
active substances are naturally soluble in oil, there is no need to add water in the second
bath and a simple formulation of the oil is sufficient. The stability of the bath is then
improved (the only concern is the oxidative stability of the oil and the active substances
since dephasing is not a possibility).

P31
Cellulases in bi-phasic media
Nathalie Berezina, Joel Nys, and Laurent Paternostre, Natiss - Materia Nova, 7822
Ghislenghien, Belgium; nathalie.berezina@materianova.be
Nowadays, cellulases are considered with great interest by White Biotechnology industry
[1]. Indeed, these enzymes are easy to produce at industrial scale, easy to use and
present promising route for second generation biofuels. The catalytic activity of common
cellulases is well known i.e. optimal pH, temperature, etc [2]. Many possible substrates
were also already tested [3]. However, only little work, at our knowledge, was done on
cellulases activity in non-aqueous media [4].
We present here a study of enzymatic activity of three different commercial cellulases from
A. niger, Aspergillus sp. and Trichoderma virens in various biphasic, organic solvent /
buffer, conditions.
We found that the A. niger cellulases had the best catalytic activity in a biphasic media
containing up to 75 % of chloroform phase. In this case up to 40 g/L cellulose contained in
buffer phase can be transformed in 4 hours by 10 g/L overall enzyme.
-------
1. a) Lin Y., Tanaka S., Appl. Microbiol. Biotechnol., 2006, 69-6, 627; b) Percival Zhang
Y.H., Himmel M.E., Mielenz J.R., Biotechnol. Adv., 2006, 24-5, 452
2. a) Castellanos O.F., Sinitsyn A.P., Vlasenko E.Yu., Bioressource Technology, 1995, 52,
119; b) Duff S.J.B., Cooper D.G., Fuller O.M., Enzyme Microb. Technol., 1986, 8, 305
3. a) Claeyssens M., Aerts G., Bioressource Technology, 1992, 39, 143; b) Walker L.P.,
Wilson D.B., Irwin D.C., Enzyme Microb. Technol., 1990, 12, 378; c) Castellanos O.F.,
Sinitsyn A.P., Vlasenko E.Yu., Bioressource Technology, 1995, 52, 109;
4. a) Chen N., Fan J.B., Xiang J., Chen J., Liang Y., Biochim. Biophys. Acta, 2006, 1764-6,
1029; b) Woodward C.A., Kaufman E.N., Biotechnol. Bioeng., 1996, 52-3, 423; c)
Kilpeläinen I., Xie H., King A., Granstrom M., Heikkinen S., Argyropoulos D.S., J. Agric.
Food Chem., 2007, 55-22, 9142
75

List of participants
Prof. Dr. Joel Barrault
CNRS/LACCO
avenue du recteur pineau 40
86022 Poitiers, France
joel.barrault@univ-poitiers.fr
Mr. Fabio Bassetto
Breton SPA
via Garibaldi 27
31030 Castello di Godego, Italy
bassetto.fabio@breton.it
Dr. Franz-Erich Baumann
Evonik-Degussa GmbH
Paul-Baumann-Str. 1
45764 Marl Germany
margret.bueckers@evonik.com
Mr. Jens Baumgard
LIKAT Rostock
Albert- Einstein Straße 29a
18059 Rostock, Germany
jens.baumgard@catalysis.de
Dr. Nathalie Berezina
Natiss - Materia Nova
rue des Foudriers 1
7822 Ghislenghien, Belgium
nathalie.berezina@materianova.be
Mrs. Tanja Van Bergen-Brenkman
Croda
Buurtje 1
2802BE Gouda, Netherlands
tanja.van.bergen@croda.com
Mr. Avinash Bhadani
Guru Nanak Dev University
143005 Amritsar, India
avinashbhadani2003@yahoo.co.in
Dr. Ursula Biermann
University of Oldenburg
Carl-von-Ossietzky-Str. 9-11
26111 Oldenburg, Germany
ursula.biermann@uni-oldenburg.de
76
Dr. Michael Blumenstein
HOBUM Oleochemicals GmbH
Seehafenstraße 20
21079 Hamburg, Germany
pknolle@hobum.de
Dr. Christian Bruneau
Sciences Chimiques
Avenue du General Leclerc 263
35042 Rennes, France
christian.bruneau@univ-rennes1.fr
Dr. Laure Candy
Laboratoire de Chimie AgroIndustrielle;
ENSIACET
Route de Narbonne 118
31077 Toulouse, France
laure.candy@ensiacet.fr
Dr. Gökhan Çaylı
Koç University
Rumelifeneri yolu 0
34450 Istanbul, Turkey
gcayli@ku.edu.tr
Prof. Dr. David J. Cole-Hamilton
University of St. Andrews, School of
Chemistry
North Haugh KY169ST
St. Andrews, United Kingdom
djc@st-and.ac.uk
Dr. Ralf Collenburg
Thywissen GmbH
Industriestr. 34
41460 Neuss, Germany
ralf.collenburg@cthywissenoel.de
Dr. Manfred Diedering
Alberdingk Boley GmbH
Düsseldorfer Strasse 39
47829 Krefeld, Germany
m.diedering@alberdingk-boley.de
Mr. Guy B. Djigoue
FH-OOW
Constantiaplatz 4
26723 Emden, Germany
djigoue@yahoo.fr

Mr. Lucas Montero de Espinosa
Universitat Rovira i Virgili
Marcel.li Domingo
43007 Tarragona, Spain
lucas.montero@urv.cat
Dr. Patrice A. Fokou
FH-OOW
Constantiaplatz 4
26723 Emden, Germany
patrice.fokou@fh-oow.de
Dr. Thomas Früh
Lanxess Deutschland GmbH
Chempark Leverkusen, Q 18 Raum 1755
51369 Leverkusen, Germany
thomas.frueh@lanxess.com
Prof. Dr. Annett Fuchs
Hochschule Zittau/Görlitz
Theodor-Körner-Allee 16
02763 Zittau, Germany
a.fuchs@hs-zigr.de
Dr. Marina Galià
University Rovira i Virgili
Marcel.li Domingo
43007 Tarragona, Spain
marina.galia@urv.cat
Mr. Dominik Geisker
FH-OOW
Constantiaplatz 4
26723 Emden, Germany
dominik.geisker@fh-oow.de
Dr. Torsten Germer
Robert Kraemer
Zum Roten Hahn 9
26180 Rastede, Germany
sekretariat@rokra.com
Dr. Allan Green
CSIRO Plant Industry
PO Box 1600
2601 Canberra, Australia
allan.green@csiro.au
Prof. Dr. Dieter Greif
Hochschule Zittau/Görlitz
Theodor-Körner-Allee 16
02763 Zittau, Germany
d.greif@hs-zigr.de
Dr. Sarina Grinberg
Ben-Gurion University
Hashalom 1
84105 Beer-Sheva, Israel
sarina@bgu.ac.il
Dr. Matteo Guidotti
CNR-ISTM
via Venezian 21
20133 Milano, Italy
m.guidotti@istm.cnr.it
Dr. Harald Haeger
Evonik Degussa GmbH
Paul-Baumann-Str. 1
45764 Marl Germany
margret.bueckers@evonik.com
Dr. Peter Hannen
Evonik Degussa GmbH
Paul-Baumann-Str. 1
45764 Marl Germany
margret.bueckers@evonik.com
Mrs. Katharina Heidkamp
Johann Heinrich von Thünen-Institut (vTI)
Bundesallee 50
38116 Braunschweig, Germany
katharina.heidkamp@vti.bund.de
Dr. Karlheinz Hill
Cognis GmbH
Rheinpromenade 1
40789 Monheim, Germany
Karlheinz.Hill@cognis.com
Dr. Norbert Holst
Fachagentur Nachwachsende Rohstoffe
Hofplatz 1
18276 Gülzow, Germany
n.holst@fnr.de
77

Mr. Rachid Ihizane
Universität Wuppertal
Gaußstr. 20
42119 Wuppertal, Germany
ihizane@uni-wuppertal.de
Prof. Dr. Rosa Infante
CSIC
Jordi Girona 18
08034 Barcelona, Spain
rimste@cid.csic.es
Dr. Guido Jach
Phytowelt GreenTechnologies GmbH
Kölsumer Weg 33
41334 Nettetal, Germany
contact@phytowelt.com
Mrs. Tina Jacobs
FH-OOW
Constantiaplatz 4
26723 Emden, Germany
tina.jacobs@fho-emden.de
Mr. Swapnil R. Jadhav
City College of City University of New
York
160 Convent Avenue 137 St
10031 New York, United States
sjadhav@gc.cuny.edu
Dr. Bernd Jakob
Universität Wupeprtal
Gausstr. 20
42097 Wuppertal, Germany
bjakob@uni-wuppertal.de
Dr. François Jérôme
CNRS/LACCO
avenue du recteur Pineau 40
86022 Poitiers, France
francois.jerome@univ-poitiers.fr
Prof. Dr. George John
The City College of CUNY
1237 Marshak Hall, 160 Convent Avenue
138 Street
10031 New York, United States
john@sci.ccny.cuny.edu
78
Mr. Pavels Karabesko
Riga Technical University
Azenes 22a-422b
LV-1048 Riga, Latvia
pave23@inbox.lv
Mrs. Melanie Kellermann
Hochschule Zittau/Görlitz
Theodor-Körner-Allee 16
02763 Zittau, Germany
m.kellermann@hs-zigr.de
Mrs. Manuela Kniese
FH-OOW
Constantiaplatz 4
26723 Emden, Germany
manuela.kniese@gmx.de
Mr. Kristian Kowollik
Fraunhofer Institut für Chemische
Technologie
Joseph-von-Fraunhoferstrasse 7
76327 Pfinztal, Germany
kristian.kowollik@ict.fraunhofer.de
Mr. Dieter Kundrun
American Soybean Association
Cuxhavener Str. 454c
21149 Hamburg, Germany
dkundrun@aol.com
Dr. Andreas Kunst
BASF SE
Carl-Bosch-Str. 38
67056 Ludwigshafen, Germany
andreas.kunst@basf.com
Prof. Dr. Selim H. Kusefoglu
Bogazici University
Etiler 0000
34342 Istanbul, Turkey
kusef@boun.edu.tr
Dr. Andreas Martin
Leibniz-Institut für Katalyse
R.-Willstätter-Str. 12
12489 Berlin Germany
andreas.martin@catalysis.de

Dr. Michael A. R. Meier
FH-OOW
Constantiaplatz 4
26723 Emden, Germany
michael.meier@fh-oow.de
Prof. Dr. Jürgen O. Metzger
abiosus e.V.
Bloherfelder Str. 239
26129 Oldenburg, Germany
metzger@abiosus.org
Mrs. Xiaowei Miao
Institut Sciences Chimiques de Rennes
avenue du Général Leclerc 263
35042 Rennes, France
mxw331@yahoo.com
Mr. Jordi Morros
IQAC - CSIC
Jordi Girona 18-26
08034 Barcelona, Spain
jmcste@cid.csic.es
Mrs. Hatice Mutlu
FH-OOW
Constantiaplatz 4
26723 Emden, Germany
hatice.mutlu@fh-oow.de
Mr. Cem Öztürk
Bogazici University, Chemistry
Department
Kare Blok Kuzey Kampus Bebek
34342 Istanbul, Turkey
cem34@yahoo.com
Mr. Dirk Packet
Oleon
Vaartstraat 130
B-2520 Oelegem, Belgium
dirk.packet@oleon.com
Mr. Mazeyar Parvinzadeh
Islamic Azad University, Shahre rey
branch
Pasdaran street No.5
Tehran, Islamic Republic of Iran
mpgconf@gmail.com
Mrs. Jessica Pérez Gomes
Technische Universität Dortmund
Emil-Figge-Strasse 66
44227 Dortmund, Germany
jessica.perez-gomes@bci.unidortmund.de
Prof. Dr. Zoran S. Petrovic
Pittsburg State University, Kansas
Polymer Research Center
S. Broadway 1701
66762 Pittsburg, KS, United States
zpetrovi@pittstate.edu
Mr. Jürgen Pettrak
TU München
Schulgasse 16
94315 Straubing, Germany
juergen.pettrak@wzw.tum.de
Dr. H.J.F.(Erik) Philipse
Croda
PO Box 2
2800 AA Gouda, Netherlands
erik.philipse@croda.com
Mrs. Renate Polster
HOBUM Oleochemicals GmbH
Seehafenstraße 20
21079 Hamburg, Germany
pknolle@hobum.de
Dr. Ulf Prüße
Johann Heinrich von Thünen-Institut (vTI)
Bundesallee 50 38116
Braunschweig, Germany
ulf.pruesse@vti.bund.de
Dr. Yann M. Raoul
SIA
Avenue George V 12
75008 Paris, France
y.raoul@prolea.com
Mr. Enrique del Rio
University Rovira i Virgili
marcelli domingo
43007 Tarragona, Spain
enrique.delrio@urv.cat
79

Dr. Rita Rosenbaum
HOBUM Oleochemicals GmbH
Seehafenstraße 20
21079 Hamburg, Germany
pknolle@hobum.de
Mr. Jesus Santamaria
MERQUINSA
GRAN VIAL 17
08160 MONTMELO BARCELONA,
Spain
AHALL@MERQUINSA.COM
Prof. Dr. Hans J. Schäfer
Universität Münster-Organisch-
Chemisches Institut
Correns-Str. 40
48149 Münster, Germany
schafeh@uni-muenster.de
Prof. Dr. Manfred P. Schneider
Bergische Universität
Gauss-Strasse 20
42097 Wuppertal, Germany
schneid@uni-wuppertal.de
Mr. Tim Sieker
University of Kaiserslautern
Gottlieb-Daimler-Straße 44
67663 Kaiserslautern, Germany
tim.sieker@mv.uni-kl.de
Mr. Aleksejs Smirnovs
Riga Technical University
azenes street 22a - 811a
Lv-1048 Riga, Latvia
aleksejs86@inbox.lv
Prof. Andrzej Sobkowiak
Rzeszow University of Technology
W. Pola 2
35-959 Rzeszow, Poland
asobkow@prz.edu.pl
Dr. Kirstin Suck
Süd-Chemie AG
Ostenrieder Str. 15
85368 Moosburg, Germany
kirstin.suck@sud-chemie.com
80
Mrs. Ediz Taylan
Bogazici University Bebek
34342 Istanbul, Turkey
etaylan@boun.edu.tr
Mrs. Maike Tober
Universität Hamburg, Institut für
Organische Chemie
Martin-Luther-King-Platz 6
20146 Hamburg Germany
tober@chemie.uni-hamburg.de
Dr. Peter J. Tollington
CRODA
BUURTJE 1
2802BE GOUDA, Netherlands
peter.tollington@croda.com
Prof. Dr. Wilfried Umbach
Bockumer Str. 143
40489 Düsseldorf, Germany
wilfried.umbach@t-online.de
Dr. Tomas Vlcek
SYNPO, a.s.
S. K. Neumanna 1316
532 07 Pardubice, Czech Republic
tomas.vlcek@synpo.cz
Dr. Paul Wagner
Lanxess Deutschland GmbH
Chempark Leverkusen, Q18
51369 Leverkusen, Germany
paul.wagner@lanxess.com
Dr. Sandra Warren
ITERG
Rue Gasparg Monge 11
33600 Pessac, France
s.warren@iterg.com
Dr. Ralf Weberskirch
BayerMaterialScience AG
Kaiser-Wilhlem Allee 1
51368 Leverkusen, Germany
ralf.weberskirch@bayerbms.com

Dr. Alfred Westfechtel
Cognis Oleochemicals GmbH
Henkelstr. 67
40551 Düsseldorf, Germany
liane.momm@cognis-oleochemicals.com
Mr. Stefano Zeggio
Breton SPA
via Garibaldi 27
31030 Castello di Godego, Italy
zeggio.stefano@breton.it
Mrs. Tamara Zietek
Phytowelt GreenTechnologies GmbH
Kölsumer Weg 33
41334 Nettetal, Germany
contact@phytowelt.com
Dr. Fernando Zuniga
Cognis Oleochemicals GmbH
Henkelstr. 67
40551 Düsseldorf, Germany
liane.momm@cognis-oleochemicals.com
81